Compound containing 1,3-diene structure and method for producing same

ABSTRACT

Disclosed is a compound containing a divalent group represented by formula (I). (In formula (I), Ar 1  represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group; J 1  represents a phenylene group; J 2  represents an alkylene group; X represents an oxygen atom or a sulfur atom; j represents 0 or 1, k represents an integer of 0-3, and l represents 0 or 1, while satisfying 1≦j+k+l≦5; m represents 1 or 2; R 1  represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, a carbamoyl group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group; the plurality of R 1 &#39;s may be the same as or different from each other; and when there are a plurality of J 1 &#39;s, J 2 &#39;s, X&#39;s, j&#39;s, k&#39;s or l&#39;s, the J 1 &#39;s, J 2 &#39;s, X&#39;s, j&#39;s, k&#39;s or l&#39;s may be the same as or different from each other, respectively).

This application is a National Stage of International Application No. PCT/JP2009/063457 filed Jul. 29, 2009, claiming priority based on Japanese Patent Application No. 2008-194523 filed Jul. 29, 2008, the contents of all of which are incorporated herein by reference in their entirety.

TECHNICAL FIELD

The present invention relates to a compound containing a 1,3-diene structure and a method for producing the same.

BACKGROUND ART

A high molecular-weight light-emitting material and a charge transport material are useful as e.g., a material for use in an organic layer of a light-emitting device and thus have been studied in various ways. As the material above, for example, a compound that can be hardened by crosslinking a benzocyclobutene residue for producing a layered light-emitting device (Patent Literatures 1 and 2) and a compound having two olefins (non-conjugated diene) useful for producing a layered light-emitting device (Patent Literature 3) have been proposed.

CITATION LIST Patent Literature

-   Patent Literature 1: International Publication No. WO2005/049689 -   Patent Literature 2: JP 2008-106241 A -   Patent Literature 3: International Publication No. WO2004/093154

SUMMARY OF INVENTION Technical Problem

However, the aforementioned compound is insufficient in harden ability.

In the circumstances, an object of the present invention is to provide a compound showing an excellent harden ability.

Solution to Problem

The present invention firstly provides a compound comprising a divalent group represented by the following formula (I):

wherein Ar¹ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group; J¹ represents a phenylene group; J² represents an alkylene group; X represents an oxygen atom or a sulfur atom; j is 0 or 1, k is an integer of 0 to 3 and l is 0 or 1, such that l≦j+k+l≦5; m is 1 or 2; R¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, a carbamoyl group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group; a plurality of R¹ may be the same or different; and a plurality of J¹, J², X, j, k and l each may be the same or different.

The present invention secondly provides a composition comprising at least one selected from the group consisting of a hole transport material, an electron transport material and a light-emitting material, and the aforementioned compound.

The present invention thirdly provides a liquid composition containing the aforementioned compound and a solvent.

The present invention fourthly provides a film containing the aforementioned compound and a film formed by crosslinking the aforementioned compound.

The present invention fifthly provides a light-emitting device having electrodes comprising an anode and a cathode and an organic layer provided between the electrodes and containing the aforementioned compound.

The present invention sixthly provides a surface light source and a display having the aforementioned light-emitting device.

The present invention seventhly provides an organic transistor and organic photoelectric transducer formed by using the aforementioned compound.

The present invention eighthly provides a compound represented by the following formula (X):

wherein Ar¹ is an arylene group, a divalent heterocyclic group or a divalent aromatic amine group; J¹ represents a phenylene group, J² represents an alkylene group; X represents an oxygen atom or a sulfur atom; X¹ and X² each independently represent a halogen atom; k is an integer of 0 to 3, l is 0 or 1 and m is 1 or 2; and a plurality of J¹, J², X, k and l each may be the same or different.

The present invention ninthly provides a method for producing a compound represented by the above formula (X), comprising reacting, in a base, a compound represented by the following formula (XI):

wherein Ar¹ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group; J¹ represents a phenylene group; X represents an oxygen atom or a sulfur atom; X¹ and X² each independently represent a halogen atom; k is an integer of 0 to 3, l is 0 or 1 and m is 1 or 2; and a plurality of J¹, X, k and l each may be the same or different, and a compound represented by the following formula (XII):

wherein X³ represents a halogen atom; and J² represents an alkylene group.

Advantageous Effects of Invention

The compound of the present invention is a compound showing an excellent harden ability (for example, thermosetting property).

DESCRIPTION OF EMBODIMENTS

The present invention will be more specifically described below. Note that, in the specification, a diene structure such as a structure represented by the following formula:

wherein R¹ is the same as defined above, is expressed by E-form; however, a diene structure may be E-form, Z-form or a mixture thereof.

<Compound>

The compound of the present invention is a compound comprising a divalent group represented by the above formula (I); however, in view of heat resistance, it is preferably a polymer compound comprising a divalent group represented by the above formula (I) and more preferably a polymer compound having a divalent group represented by the above formula (I) as a repeating unit. Furthermore, the compound of the present invention, in view of harden ability, may have two or more types of divalent groups represented by the above formula (I) as a repeating unit.

Furthermore, the compound of the present invention is preferably a polymer compound in view of the charge transport property and luminescence property of a crosslinked film, and easiness of forming a film from a solution.

The compound of the present invention may be either a low molecular compound or a polymer compound. The low molecular compound refers to a compound having a molecular weight of 1×10¹ or more and less than 1×10³. Furthermore, the low molecular compound usually has a single molecular weight. Whereas, a polymer compound refers to a compound having a polystyrene-equivalent number average molecular weight of 1×10³ to 1×10⁸. Furthermore, a polymer compound has a molecular-weight distribution.

In the above formula (I), Ar¹ is preferably an arylene group in view of durability; in view of charge transport property, a divalent heterocyclic group is preferred.

In the above formula (I), the arylene group represented by Ar¹, is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. Examples thereof include an arylene group having a condensed ring and an arylene group to which an independent benzene ring or two or more condensed rings are bonded directly or via a vinylene group or the like. The arylene group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group and a nitro group. In view of solubility, fluorescence property, easiness of synthesis and characteristics of the device to be obtained, etc. an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a halogen atom or a cyano group is preferable.

In the arylene group represented by Ar¹, the number of carbon atoms of a moiety excluding a substituent is usually 6 to 60 and preferably 6 to 20, and the total number of carbon atoms of a moiety including the substituent is usually 6 to 100.

Examples of the arylene group represented by Ar¹ include a phenylene group (as shown in the following formulas 1 to 3), a naphthalenediyl group (as shown in the following formulas 4 to 13), an anthracene-diyl group (as shown in the following formulas 14 to 19), a biphenyl-diyl group (as shown in the following formulas 20 to 25), a terphenyl-diyl group (as shown in the following formulas 26 to 28), a condensed ring compound group (as shown in the following formulas 29 to 35), a fluorene-diyl group (as shown in the following formulas 36 to 38) and a benzofluorene-diyl (as shown in the following formulas 39 to 46). In view of durability, a phenylene group, a naphthalenediyl group, an anthracene-diyl group, a biphenyl-diyl group, a fluorene-diyl group and a benzofluorene-diyl group are preferable; a naphthalenediyl group, an anthracene-diyl group, a biphenyl-diyl group, a fluorene-diyl group and a benzofluorene-diyl group are more preferable; a naphthalenediyl group, an anthracene-diyl group, a fluorene-diyl group and a benzofluorene-diyl group are further preferable; a fluorene-diyl group and a benzofluorene-diyl group are particularly preferable; and a fluorene-diyl group is the most preferable. Furthermore, as the arylene group represented by Ar¹, in view of easiness of synthesizing the compound to be obtained, a phenylene group and a fluorene-diyl group are preferable, p-phenylene, m-phenylene and 2,7-fluorene-diyl groups are more preferable, and p-phenylene and 2,7-fluorene-diyl groups are particularly preferable. Note that the following groups may have a substituent.

The alkyl group serving as a substituent as mentioned above may be any one of linear, branched and cyclic alkyl groups and may have a substituent. Such an alkyl group usually has 1 to 20 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a 3,7-dimethyloctyl group, a lauryl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group and a perfluorooctyl group.

The alkoxy group serving as a substituent as mentioned above may be any one of linear, branched and cyclic alkoxy groups and may have a substituent. Such an alkoxy group usually has 1 to 20 carbon atoms. Examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, a lauryloxy group, a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, a perfluorooctyloxy group, a methoxymethyloxy group and a 2-methoxyethyloxy group.

The alkylthio group serving as a substituent as mentioned above may be any one of linear, branched and cyclic alkylthio groups and may have a substituent. Such an alkylthio group usually has about 1 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a t-butylthio group, a pentylthio group, a hexylthio group, a cyclohexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group and a trifluoromethylthio group.

The aryl group serving as a substituent as mentioned above is an atomic group, which is obtained by removing a single hydrogen atom from an aromatic hydrocarbon, includes an aryl group having a condensed ring, an aryl group to which an independent benzene ring or two or more condensed rings are bonded directly or via a vinylene group or the like. The aryl group usually has 6 to 60 carbon atoms and preferably 7 to 48 carbon atoms. Examples thereof include a phenyl group, a C₁ to C₁₂ alkoxyphenyl group (“C₁ to C₁₂ alkoxy” means that the number of carbon atoms of the alkoxy moiety is 1 to 12. The same is applied hereinafter), a C₁ to C₁₂ alkylphenyl group (“C₁ to C₁₂ alkyl” means that the number of carbon atoms of the alkyl moiety is 1 to 12. The same is applied hereinafter), a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group and a pentafluorophenyl group; and preferably a C₁ to C₁₂ alkoxyphenyl group and a C₁ to C₁₂ alkylphenyl group.

Examples of the C₁ to C₁₂ alkoxyphenyl group include a methoxyphenyl group, an ethoxyphenyl group, a propyloxyphenyl group, an isopropyloxyphenyl group, a butoxyphenyl group, an isobutoxyphenyl group, a t-butoxyphenyl group, a pentyloxyphenyl group, a hexyloxyphenyl group, a cyclohexyloxyphenyl group, a heptyloxyphenyl group, an octyloxyphenyl group, a 2-ethylhexyloxyphenyl group, a nonyloxyphenyl group, a decyloxyphenyl group, a 3,7-dimethyloctyloxyphenyl group and a lauryloxyphenyl group.

Examples of the C₁ to C₁₂ alkylphenyl group include a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a propylphenyl group, a mesityl group, a methylethylphenyl group, an isopropylphenyl group, a butylphenyl group, an isobutylphenyl group, a t-butylphenyl group, a pentylphenyl group, an isoamylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group and a dodecylphenyl group.

The aryloxy group serving as a substituent as mentioned above usually has 6 to 60 carbon atoms and preferably 7 to 48 carbon atoms. Examples of the aryloxy group include a phenoxy group, a C₁ to C₁₂ alkoxyphenoxy group, a C₁ to C₁₂ alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group and a pentafluorophenyloxy group; and preferably a C₁ to C₁₂ alkoxyphenoxy group and a C₁ to C₁₂ alkylphenoxy group.

Examples of the C₁ to C₁₂ alkoxyphenoxy group include a methoxyphenoxy group, an ethoxyphenoxy group, a propyloxyphenoxy group, an isopropyloxyphenoxy group, a butoxyphenoxy group, an isobutoxyphenoxy group, a t-butoxyphenoxy group, a pentyloxyphenoxy group, a hexyloxyphenoxy group, a cyclohexyloxyphenoxy group, a heptyloxyphenoxy group, an octyloxyphenoxy group, a 2-ethylhexyloxyphenoxy group, a nonyloxyphenoxy group, a decyloxyphenoxy group, a 3,7-dimethyloctyloxyphenoxy group and a lauryloxyphenoxy group.

Examples of the C₁ to C₁₂ alkylphenoxy group include a methylphenoxy group, an ethylphenoxy group, a dimethylphenoxy group, a propylphenoxy group, a 1,3,5-trimethylphenoxy group, a methylethylphenoxy group, an isopropylphenoxy group, a butylphenoxy group, an isobutylphenoxy group, a t-butylphenoxy group, a pentylphenoxy group, an isoamylphenoxy group, a hexylphenoxy group, a heptylphenoxy group, an octylphenoxy group, a nonylphenoxy group, a decylphenoxy group and a dodecylphenoxy group.

The arylthio group serving as a substituent as mentioned above may have a substituent on the aromatic ring and usually has about 3 to 60 carbon atoms. Specific examples thereof include a phenylthio group, a C₁ to C₁₂ alkoxyphenylthio group, a C₁ to C₁₂ alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group and a pentafluorophenylthio group.

The arylalkyl group serving as a substituent as mentioned above may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C₁ to C₁₂ alkyl group, a C₁ to C₁₂ alkoxyphenyl-C₁ to C₁₂ alkyl group, a C₁ to C₁₂ alkylphenyl-C₁ to C₁₂ alkyl group, a 1-naphthyl-C₁ to C₁₂ alkyl group and a 2-naphthyl-C₁ to C₁₂ alkyl group.

The arylalkoxy group serving as a substituent as mentioned above may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C₁ to C₁₂ alkoxy group, a C₁ to C₁₂ alkoxyphenyl-C₁ to C₁₂ alkoxy group, a C₁ to C₁₂ alkylphenyl-C₁ to C₁₂ alkoxy group, a 1-naphthyl-C₁ to C₁₂ alkoxy group and a 2-naphthyl-C₁ to C₁₂ alkoxy group.

The arylalkylthio group serving as a substituent as mentioned above may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C₁ to C₁₂ alkylthio group, a C₁ to C₁₂ alkoxyphenyl-C₁ to C₁₂ alkylthio group, a C₁ to C₁₂ alkylphenyl-C₁ to C₁₂ alkylthio group, a 1-naphthyl-C₁ to C₁₂ alkylthio group and a 2-naphthyl-C₁ to C₁₂ alkylthio group.

The arylalkenyl group serving as a substituent as mentioned above usually has about 8 to 60 carbon atoms. Specific examples thereof include a phenyl-C₂ to C₁₂ alkenyl group, a C₁ to C₁₂ alkoxyphenyl-C₂ to C₁₂ alkenyl group, a C₁ to C₁₂ alkylphenyl-C₂ to C₁₂ alkenyl group, a 1-naphthyl-C₂ to C₁₂ alkenyl group and a 2-naphthyl-C₂ to C₁₂ alkenyl group. A C₁ to C₁₂ alkoxyphenyl-C₂ to C₁₂ alkenyl group and a C₁ to C₁₂ alkylphenyl-C₂ to C₁₂ alkenyl group are preferable.

The arylalkynyl group serving as a substituent as mentioned above usually has about 8 to 60 carbon atoms. Specific examples thereof include a phenyl-C₂ to C₁₂ alkynyl group, a C₁ to C₁₂ alkoxyphenyl-C₂ to C₁₂ alkynyl group, a C₁ to C₁₂ alkylphenyl-C₂ to C₁₂ alkynyl group, a 1-naphthyl-C₂ to C₁₂ alkynyl group and a 2-naphthyl-C₂ to C₁₂ alkynyl group. A C₁ to C₁₂ alkoxyphenyl-C₂ to C₁₂ alkynyl group and a C₁ to C₁₂ alkylphenyl-C₂ to C₁₂ alkynyl group are preferable.

The substituted amino group serving as a substituent as mentioned above may be an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituted amino group excluding the number of carbon atoms of a substituent is usually about 1 to 60 and preferably 2 to 48 carbon atoms.

Specific examples thereof include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a propylamino group, a dipropylamino group, an isopropylamino group, a diisopropylamino group, a butylamino group, an s-butylamino group, an isobutylamino group, a t-butylamino group, a pentylamino group, a hexylamino group, a cyclohexylamino group, a heptylamino group, an octylamino group, a 2-ethylhexylamino group, a nonylamino group, a decylamino group, a 3,7-dimethyloctylamino group, a laurylamino group, a cyclopentylamino group, a dicyclopentylamino group, a dicyclohexylamino group, a pyrrolidyl group, a piperidyl group, a ditrifluoromethylamino group, a phenylamino group, a diphenylamino group, a C₁ to C₁₂ alkoxyphenylamino group, a di(C₁ to C₁₂ alkoxyphenyl)amino group, a di(C₁ to C₁₂ alkylphenyl)amino group, a 1-naphthylamino group, a 2-naphthylamino group, a pentafluorophenylamino group, a pyridylamino group, a pyridazinylamino group, a pyrimidylamino group, a pyrazylamino group, a triazylamino group, a phenyl-C₁ to C₁₂ alkylamino group, a C₁ to C₁₂ alkoxyphenyl-C₁ to C₁₂ alkylamino group, a C₁ to C₁₂ alkylphenyl-C₁ to C₁₂ alkylamino group, a di(C₁ to C₁₂ alkoxyphenyl-C₁ to C₁₂ alkyl)amino group, a di(C₁ to C₁₂ alkylphenyl-C₁ to C₁₂ alkyl)amino group, a 1-naphthyl-C₁ to C₁₂ alkylamino group and a 2-naphthyl-C₁ to C₁₂ alkylamino group.

The substituted silyl group serving as a substituent as mentioned above may be a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The number of carbon atoms of the substituted silyl group is usually about 1 to 60 and preferably 3 to 48. Note that the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.

Specific examples thereof include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tri-isopropylsilyl group, a dimethyl-isopropylsilyl group, a diethyl-isopropylsilyl group, a t-butyldimethylsilyl group, a pentyldimethylsilyl group, a hexyldimethylsilyl group, a heptyldimethylsilyl group, an octyldimethylsilyl group, a 2-ethylhexyl-dimethylsilyl group, a nonyldimethylsilyl group, a decyldimethylsilyl group, a 3,7-dimethyloctyl-dimethylsilyl group, a lauryldimethylsilyl group, a phenyl-C₁ to C₁₂ alkylsilyl group, a C₁ to C₁₂ alkoxyphenyl-C₁ to C₁₂ alkylsilyl group, a C₁ to C₁₂ alkylphenyl-C₁ to C₁₂ alkylsilyl group, a 1-naphthyl-C₁ to C₁₂ alkylsilyl group, a 2-naphthyl-C₁ to C₁₂ alkylsilyl group, a phenyl-C₁ to C₁₂ alkyldimethylsilyl group, a triphenylsilyl group, a tri-p-xylylsilyl group, a tribenzylsilyl group, a diphenylmethylsilyl group, a t-butyldiphenylsilyl group and a dimethylphenylsilyl group.

Examples of a halogen atom serving as a substituent as mentioned above include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The acyl group serving as a substituent as mentioned above usually has about 2 to 20 carbon atoms and preferably 2 to 18 carbon atoms. Specific examples thereof include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group and a pentafluorobenzoyl group.

The acyloxy group serving as a substituent as mentioned above usually has about 2 to 20 carbon atoms and preferably 2 to 18 carbon atoms. Specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group and a pentafluorobenzoyloxy group.

The imine residue serving as a substituent as mentioned above refers to a residue obtained by removing a single hydrogen atom from an imine compound (which refers to an organic compound having —N═C— in the molecule. Examples thereof include aldimine, ketimine and a compound obtained by substituting a hydrogen atom on N of these with e.g., an alkyl group) and usually has about 2 to 20 carbon atoms and preferably 2 to 18 carbon atoms. Specific examples include groups represented by the following structural formulas.

The carbamoyl group serving as a substituent as mentioned above usually has about 2 to 20 carbon atoms and preferably 2 to 18 carbon atoms. Specific examples thereof include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group and a dipentafluorobenzamide group.

Examples of the acid imide group serving as a substituent as mentioned above include a residue obtained by removing a hydrogen atom bound to the nitrogen atom of the acid imide and having about 4 to 20 carbon atoms. Specific examples thereof include the groups shown below.

The monovalent heterocyclic group serving as a substituent as mentioned above refers to a remaining atomic group obtained by removing a single hydrogen atom from a heterocyclic compound and usually having about 4 to 60 carbon atoms and preferably 4 to 20 carbon atoms. Of the monovalent heterocyclic groups, a monovalent aromatic heterocyclic group is preferable. Note that the number of carbon atoms of a substituent is not included in the number of carbon atoms of a heterocyclic group. The heterocyclic compound herein refers to an organic compound having a ring structure, which is not only constituted of a carbon atom but also contains a hetero atom such as oxygen, sulfur, nitrogen, phosphorus and boron, within the ring. Specific examples thereof include a thienyl group, a C₁ to C₁₂ alkylthienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C₁ to C₁₂ alkylpyridyl group, a piperidyl group, a quinolyl group and an isoquinolyl group. A thienyl group, a C₁ to C₁₂ alkyl thienyl group, a pyridyl group and a C₁ to C₁₂ alkyl pyridyl group are preferable.

Examples of the substituted carboxyl group serving as a substituent as mentioned above refers to a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group and usually having about 2 to 60 carbon atoms and preferably 2 to 48 carbon atoms. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a t-butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, a 3,7-dimethyloctyloxycarbonyl group, a dodecyloxycarbonyl group, a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, a perfluorooctyloxycarbonyl group, a phenoxycarbonyl group, a naphthoxycarbonyl group and a pyridyloxycarbonyl group. Note that the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituent is not included in the number of carbon atoms of the substituted carboxyl group.

In the above formula (I), the divalent heterocyclic group represented by Ar¹ refers to the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound. The divalent heterocyclic group may have a substituent.

The heterocyclic compound refers to an organic compound having a ring structure, which is not only constituted of a carbon atom but also contains a hetero atom such as oxygen, sulfur, nitrogen, phosphorus, boron and arsenic within a ring. As the divalent heterocyclic group, a divalent aromatic heterocyclic group is preferable. As the substituent, in view of solubility of, fluorescence property of, easiness of synthesizing the compound to be obtained and characteristic of the device to be obtained, etc., an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a halogen atom or cyano group is preferable. These groups and atoms are defined as described above.

In the divalent heterocyclic group represented by Ar¹, the number of carbon atoms of the moiety excluding a substituent is usually, 3 to 60 and the total number of carbon atoms including a substituent is usually 3 to 100.

Examples of the divalent heterocyclic group represented by Ar¹ include the following groups. Note that the following groups may have a substituent.

Divalent heterocyclic group containing a nitrogen atom as a hetero atom: a pyridine-diyl group (as shown in the following formulas 101 to 104), a diazaphenylene group (as shown in the following formulas 105 to 108), a triazine-diyl group (as shown in the following formula 109), a quinoline-diyl group (as shown in the following formulas 110 to 114), a quinoxaline-diyl group (as shown in the following formulas 115 to 119), an acridinediyl group (the following formulas 120 to 123), a bipyridyl-diyl group (the following formulas 124 to 126), a phenanthroline diyl group (the following formulas 127 and 128).

A group containing an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc. as a hetero atom and having a fluorene structure (as shown in the following formulas 129 to 136).

A 5-membered heterocyclic group containing an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, etc. as a hetero atom (as shown in the following formulas 137 to 140).

A 5-membered condensed heterocyclic group containing an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, etc. as a hetero atom (as shown in the following formulas 141 to 158).

A 5-membered heterocyclic group containing an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, etc. as a hetero atom and bound at the a position of the hetero atom to form a dimer or an oligomer (as shown in the following formulas 159 to 160).

A 5-membered heterocyclic group containing an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, etc. as a hetero atom and bound at the a position of the hetero atom to a phenyl group (as shown in the following formulas 161 to 166).

A 5-membered condensed heterocyclic group containing an oxygen atom, a sulfur atom and a nitrogen atom, etc. as a hetero atom and substituted with a phenyl group, a furyl group, a thienyl group (the following formulas 167 to 172).

A 6-membered heterocyclic group containing an oxygen atom and nitrogen atom as a hetero atom (as shown in the following formulas 173-176).

The divalent heterocyclic group represented by Ar¹ is, in view of charge transport property, preferably a divalent group represented by the following formula (II):

wherein Y represents an oxygen atom, a sulfur atom, —N(R²²)—, —O—C(R²³)(R²⁴)—, or —Si(R²⁵)(R²⁶)—; R²², R²³, R²⁴, R²⁵ and R²⁶ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an arylalkyl group; and the formula may have a substituent.

When the above formula (II) has a substituent, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group and an arylalkoxy group. These groups are the same as defined above.

In the above formula (II), in view of easiness of synthesizing the compound of the present invention, Y is preferably an oxygen atom, a sulfur atom and —N(R²²)— and more preferably an oxygen atom and —N(R²²)—.

A divalent group represented by the above formula (II) is preferably a divalent group represented by the following formula (II)-1 or the following formula (II)-2, since a particularly high charge transport property can be obtained.

wherein Y¹ represents an oxygen atom, a sulfur atom, —N(R²²)—, —O—C(R²³)(R²⁴)— or —Si(R²⁵)(R²⁶)—; and the formula may have a substituent.

wherein Y² represents an oxygen atom, a sulfur atom, —N(R²²)—, —O—C(R²³)(R²⁴)— or —Si(R²⁵)(R²⁶)—; and the formula may have a substituent.

When the above formulas (II)-1 and (II)-2 have a substituent, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group and an arylalkoxy group. These groups are the same as defined above.

In the above formula (II)-1, in view of easiness of synthesizing the compound of the present invention, Y¹ is preferably an oxygen atom, a sulfur atom, or —N(R²²)—, more preferably an oxygen atom or —N(R²²)— and particularly preferably an oxygen atom.

In the above formula (II)-2, in view of easiness of synthesizing the compound of the present invention, Y² is preferably an oxygen atom, a sulfur atom or —N(R²²)—, more preferably a sulfur atom or —N(R²²)— and particularly preferably —N(R²²)—.

The divalent aromatic amine group represented by Ar¹ refers to the remaining atomic group obtained by removing two hydrogen atoms from an aromatic amine, having usually 5 to 100 carbon atoms and preferably 15 to 60 carbon atoms. The divalent aromatic amine group may have a substituent. Note that the number of carbon atoms of a substituent is not included in the number of carbon atoms of an aromatic amine. The substituent is, in view of solubility of, fluorescence property of and easiness of synthesizing the compound to be obtained, and easiness of crosslinking a film, preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a halogen atom and cyano group. These groups and atoms are the same as defined above.

Examples of the divalent aromatic amine group represented by Ar¹ include divalent groups represented by the following formulas 201 to 210. Note that the following groups may have a substituent.

The divalent aromatic amine group represented by Ar¹ is, in view of hole transport property, preferably a divalent group represented by the following formula (III):

wherein R³ represents a hydrogen atom, an alkyl group, an alkoxy group or a substituted amino group; and five R³ may be the same or different, or a divalent group represented by the following formula (IV):

wherein R⁴ represents a hydrogen atom, an alkyl group, an alkoxy group or a substituted amino group; and ten R⁴ may be the same or different.

In the above formulas (III) and (IV), the alkyl group and alkoxy group represented by R³ and R⁴ are the same as defined above.

In the above formulas (III) and (IV), as the substituted amino group represented by R³ and R⁴, an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl group and monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituted amino group excluding the number of carbon atoms of the substituent is usually 1 to 60 and preferably 2 to 48.

The substituted amino groups represented by R³ and R⁴ are the same as defined above.

In the above formula (I), the phenylene group represented by J¹ may have a substituent. Examples of the phenylene group include an o-phenylene, m-phenylene and p-phenylene. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom and a cyano group. These groups are the same as defined above.

In the above formula (I), the alkylene group represented by J² may be a linear or branched group. Examples of the alkyllene group include methylene, 1,2-ethylene, 1,3-propylene, 1,3-butylene, 1,4-butylene, 1,3-pentylene, 1,4-pentylene, 1,5-pentylene, 1,4-hexylene, 1,6-hexylene, 1,7-heptylene, 1,6-octylene and 1,8-octylene.

In the above formula (I), X is, in view of easiness of synthesizing the compound of the present invention, preferably an oxygen atom.

In the above formula (I), in view of easiness of synthesizing the compound, j is 0 or 1 and particularly preferably 1, of the present invention.

In the above formula (I), in view of easiness of synthesizing the compound of the present invention, k is preferably an integer selected from 0 to 2 and further preferably 0 or 1.

In the above formula (I), the alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, carbamoyl group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group and nitro group represented by R¹ are the same as defined above. However, in view of harden ability, a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group and a cyano group are preferable; a hydrogen atom, an alkyl group, an aryl group and a halogen atom are more preferable; a hydrogen atom and an alkyl group are further preferable; and a hydrogen atom is particularly preferable.

Furthermore, substituent R¹ may be mutually bound to form rings.

Examples of the ring include a C₁ to C₁₀ cycloalkyl ring that may have a substituent, a C₁ to C₁₀ cycloalkenyl ring that may have a substituent, a C₆ to C₁₄ aromatic hydrocarbon ring that may have a substituent and a C₄ to C₁₄ heterocyclic ring that may have a substituent.

Examples of the cycloalkyl ring include cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane and cyclodecane.

Examples of the cycloalkenyl ring include a cycloalkenyl ring having two or more double bonds. Specific examples thereof include a cyclohexene ring, a cyclohexadiene ring and a cyclooctatriene ring.

Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring and an anthracene ring.

Examples of the heterocyclic ring include a furan ring, a tetrahydrofuran ring, a thiophene ring, a tetrahydrothiophene ring, an indole ring, a tetrahydroindole ring, an isoquinoline ring, a pyridine ring, a thiazole ring and an oxazole ring.

In the above formula (I), a group represented by the following formula (Ia):

wherein j, k, l, J¹, J² and R¹ are the same as defined above, is, in view of harden ability of the compound of the present invention, preferably a group represented by the following formula (Ib):

wherein k, l, J² and R¹ are the same as defined above, and more preferably a group represented by the following formula (Ic):

wherein k, l and J² are the same as defined above, and a group represented by the following formula (Id):

wherein k, l and J² are the same as defined above.

As the divalent group represented by the above formula (I), divalent groups represented by the following formulas (I-1) to (I-35) are mentioned.

When the compound of the present invention is a polymer compound, in view of easiness of synthesizing the polymer compound, the compound of the present invention is preferably a polymer compound having, as the group represented by the above formula (I), a repeating unit represented by the following formula (V):

wherein J¹, J², X, R¹, k, l and m are the same as defined above; and R² represents an alkyl group, an aryl group, an arylalkyl group or an arylalkoxy group.

In the above formula (V), the alkyl group, aryl group, arylalkyl group and arylalkoxy group represented by R² are the same as defined above.

When the compound of the present invention is a polymer compound, in view of harden ability of the polymer compound, the compound of the present invention may further have a repeating unit containing a crosslinking group.

The crosslinking group refers to a substituent inducing a crosslinking reaction by stimulation of heat or light.

Examples of the crosslinking group include an oxiranyl group, an oxetanyl group, a cinnamoyl group, a dienophile group and an alkynyl group.

When the compound of the present invention is a polymer compound, in view of harden ability, the polymer compound preferably has, in addition to a repeating unit represented by the above formula (I), a repeating unit represented by the following formula (A):

wherein Ar² represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group; J³ represents a direct bond, an alkylene group or a phenylene group; and n represents 1 or 2; and a plurality of J³ may be the same or different.

In the above formula (A), the arylene group, divalent heterocyclic group and divalent aromatic amine group represented by Ar² are the same as defined above. As Ar², in view of easiness of synthesizing the compound of the present invention, an arylene group and a divalent heterocyclic group are preferable, an arylene group is more preferable, a fluorene-diyl group is further preferable and a 2,7-fluorene-diyl group is particularly preferable.

In the above formula (A), the alkylene group and phenylene group represented by J³ are the same as defined above.

In the group represented by the above formula (A), it is particularly preferable that Ar² is an arylene group, J³ is a direct bond and n is 2.

When the compound of the present invention is a polymer compound, the polymer compound preferably contains, in view of harden ability, in addition to the repeating unit represented by the above formula (I), a repeating unit represented by the following formula (B):

wherein Ar³ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group; J⁴ represents a direct bond, an alkylene group or a phenylene group; R⁵ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, a carbamoyl group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group; o represents 1 or 2; a plurality of R⁵ may be the same or different; and a plurality of J⁴ may be the same or different.

In the above formula (B), the arylene group, divalent heterocyclic group and divalent aromatic amine group represented by Ar³ may be the same as defined above. As Ar³, in view of easiness of synthesizing the compound of the present invention, an arylene group and a divalent heterocyclic group are preferable, an arylene group is more preferable, a fluorene-diyl group is further preferable and 2,7-fluorene-diyl group is particularly preferable.

In the above formula (B), the alkylene group and phenylene group represented by J⁴ are the same as defined above.

In the above formula (B), the alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, carbamoyl group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or nitro group represented by R⁵ is the same as defined above. As R⁵, in view of harden ability of the compound of the present invention, a hydrogen atom and a halogen atom are preferable and a hydrogen atom is more preferable.

In the group represented by the above formula (B), it is particularly preferable that Ar^(a) is an arylene group, J⁴ is an alkylene group and o is 2.

When the compound of the present invention is a polymer compound, in view of charge transport property of the polymer compound, the compound of the present invention further preferably contains, in addition to the repeating unit represented by the above formula (I), a repeating unit represented by the following formula (C):

wherein R⁶ represents an alkyl group, an aryl group, an arylalkyl group or an arylalkoxy group; and two R⁶ may be the same or different.

In the above formula (C), the alkyl group, aryl group, arylalkyl group and arylalkoxy group represented by R⁶ are the same as defined above. As R⁶, in view of easiness of synthesizing a raw-material monomer, an alkyl group or an aryl group is preferable and an alkyl group is further preferable.

When the compound of the present invention is a polymer compound, the polymer compound may have, in view of hole transport property, in addition to the repeating unit represented by the above formula (I), one or more repeating unit selected from the group consisting of repeating units represented by the following formula (D) and repeating units represented by the following formula (E).

wherein Ar³, Ar⁴, Ar⁵ and Ar⁶ each independently represent an arylene group or a divalent heterocyclic group; Ar⁷, Ar⁸ and Ar⁹ each independently represent an aryl group or a monovalent heterocyclic group; α and β each independently represent 0 or 1; and Ar³, Ar⁴, Ar⁵, Ar⁶, Ar⁷, Ar⁸ and Ar⁹ may have a substituent.

wherein ring P and ring Q each independently represent an aromatic hydrocarbon ring; X³ represents a single bond, an oxygen atom and a sulfur atom; and R¹⁰⁰ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, a carbamoyl group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group.

In the above formula (D), the arylene group, divalent heterocyclic group, aryl group and monovalent heterocyclic group are the same as defined above.

Examples of the substituent that Ar³, Ar⁴, Ar⁵, Ar⁶, Ar⁷, Ar⁸ and Ar⁹ may have include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, a carbamoyl group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group and a nitro group.

The alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, carbamoyl group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group and nitro group are the same as defined above.

In the above formula (E), the aromatic hydrocarbon ring represents an aromatic hydrocarbon ring obtained by removing two bonds from an arylene group as mentioned above.

In the above formula (E), the alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, carbamoyl group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group and nitro group are the same as defined above.

The repeating unit represented by the above formula (D) is, in view of hole transport property, preferably a repeating unit represented by the following formula (D)-1 or (D)-2.

wherein R⁷ represents a hydrogen atom, an alkyl group or an alkoxy group; and three R⁷ may be the same or different.

wherein R⁸ represents a hydrogen atom, an alkyl group or an alkoxy group; and six R⁸ may be the same or different.

In the above formula (B)-1, the alkyl group and alkoxy group represented by R⁷ are the same as defined above.

In the above formula (B)-2, the alkyl group and alkoxy group represented by R⁸ are the same as defined above.

The repeating unit represented by the above formula (E) is, in view of hole transport property, preferably a repeating unit represented by the following formula (E)-1.

wherein R⁹ is an alkyl group, an aryl group, an arylalkyl group or an arylalkoxy group.

In the above formula (E)-1, the alkyl group, aryl group, arylalkyl group and arylalkoxy group represented by R⁷ are the same as defined above.

When the compound of the present invention is a polymer compound, in view of charge transport property of the polymer compound, the compound of the present invention may have, in addition to the repeating unit represented by the above formula (I), one or more of the repeating units represented by the following formulas (G), (H), (J) and (K).

wherein R¹⁰ represents an alkyl group, an aryl group, an arylalkyl group or an arylalkoxy group; and two R¹⁰ may be the same or different.

wherein R¹¹ represents an alkyl group, an alkoxy group, an aryl group, an arylalkyl group or an arylalkoxy group; q represents an integer selected from 0 to 4; and a plurality of R¹¹ may be the same or different.

wherein R¹² represents an alkyl group, an alkoxy group, an aryl group, an arylalkyl group or an arylalkoxy group; Z represents an oxygen atom or a sulfur atom; r is an integer of 0 to 3; and a plurality of R¹² may be the same or different.

wherein R¹³ represents an alkyl group, an alkoxy group, an aryl group, an arylalkyl group or an arylalkoxy group; s is an integer of 0 to 2; and a plurality of R¹³ may be the same or different.

In the above formula (G), the alkyl group, aryl group, arylalkyl group and arylalkoxy group represented by R¹⁰ are the same as defined above.

In the above formula (H), the alkyl group, alkoxy group, aryl group, arylalkyl group and arylalkoxy group represented by R¹¹ are the same as defined above.

In the above formula (J), the alkyl group, alkoxy group, aryl group, arylalkyl group and arylalkoxy group represented by R¹² are the same as defined above.

In the above formula (K), the alkyl group, alkoxy group, aryl group, arylalkyl group and arylalkoxy group represented by R¹³ are the same as defined above.

When the compound of the present invention is a polymer compound, in view of luminous efficiency of the resultant compound preferably has a repeating unit represented by the above formula (I), the repeating unit represented by the above formula (C) and the repeating units represented by the above formulas (D) and (E).

Furthermore, when the compound of the present invention is a polymer compound, in view of harden ability, the compound of the present invention preferably has a repeating unit represented by the above formulas (D) and (E).

When the compound of the present invention is a polymer compound, in the compound of the present invention, the uppermost ratio (molar ratio) of the repeating unit represented by the above formula (I) is usually, in view of stability of the compound, 1 relative to the total repeating units, preferably 0.5, more preferably 0.3, and most preferably 0.15. The lowermost ratio (molar ratio) is, in view of harden ability of the compound, usually 0.01, preferably 0.02, more preferably 0.05 and most preferably 0.10.

Furthermore, when the compound of the present invention is a polymer compound having the repeating unit represented by the above formula (I), the repeating unit represented by the above formula (C) and the repeating units represented by the above formulas (D) and (E), the molar ratio of the repeating unit represented by the above formula (C) is usually, 0.1 to 0.95 relative to the total repeating units and preferably 0.3 to 0.9, whereas the whole molar ratio of the repeating units represented by the above formulas (D) and (E) is usually 0.01 to 0.5 and preferably 0.05 to 0.3.

When the compound of the present invention is a polymer compound, the compound of the present invention, in view of the life property of the light-emitting device that is formed by using the compound, preferably has a polystyrene-equivalent number average molecular weight of 1×10³ to 1×10⁸, more preferably 1×10³ to 1×10⁷, further preferably 1×10⁴ to 1×10⁷ and particularly preferably 5×10⁴ to 1×10⁷.

When the compound of the present invention is a polymer compound, the compound of the present invention, in view of harden ability, preferably has a polystyrene-equivalent weight average molecular weight of 1×10³ to 1×10⁸, more preferably 1×10⁴ to 1×10⁷ and particularly preferably 1×10⁵ to 1×10⁷.

In the specification, a number average molecular weight and a weight average molecular weight were obtained by size exclusion chromatography (SEC) (trade name: LC-10Avp manufactured by Shimadzu Corporation) as a polystyrene-equivalent number average molecular weight and weight average molecular weight. Of the methods of SEC, chromatography using an organic solvent as a mobile phase is referred to as gel permeation chromatography (GPC). The polymer to be measured was dissolved in tetrahydrofuran at a concentration of about 0.5 wt % and 30 μL of the solution was loaded in GPC. As the mobile phase of GPC, tetrahydrofuran was used and allowed to flow at a rate of 0.6 mL/minute. As the column, two TSKgel SuperHM-H (manufactured by Tosoh Corporation) columns and a single TSKgel SuperH2000 (manufactured by Tosoh Corporation) column were connected in series. As the detector, a differential refractive index detector (trade name: RID-10A, manufactured by Shimadzu Corporation) was used. Measurement was performed at 40° C.

Furthermore, when the compound of the present invention is a polymer compound, the compound of the present invention may be any one of an alternating copolymer, a random copolymer, a block copolymer and a graft copolymer, or may be a polymer compound having an intermediate structure of them, for example, a random copolymer partially having a block copolymer. The compound of the present invention is, in view of fluorescence or phosphorescence quantum yield, preferably a random copolymer partially having a block copolymer, a block copolymer and a graft copolymer rather than a complete random copolymer. In the compound of the present invention, a dendrimer having a branch in the main chain and three or more terminal portions is included.

When the compound of the present invention is a polymer compound, if a polymerizable group remains as it is as a terminal group of the compound of the present invention, the luminescence property and life of the light-emitting device produced by using the compound may sometimes decrease. Because of this, the terminal group may be protected with a stable group. As the terminal group, a group having a conjugated bond continued to a conjugated structure of the main chain is preferable. For example, a group connected to an aryl group or a monovalent heterocyclic group via a carbon-carbon bond is mentioned. Alternatively, a substituent and the like described in JP 9-45478 A, Formula 10, may be mentioned.

As the compound of the present invention, polymer compounds represented by the following formulas are mentioned. Note that v, w, x, y, z in the formulas represent composition ratios (molar ratios) of individual repeating units.

As the compound of the present invention, low molecular compounds represented by the following formulas are mentioned.

Next, a method for producing the compound of the present invention will be described, taking the case where the compound of the present invention is a polymer compound as an example.

The compound may be manufactured in any method, for example, by condensation polymerization of a compound represented by the formula: Z¹-A¹-Z². Note that in the above formula, A¹ represents a repeating unit represented by the above formula (I). Furthermore, in the above formula, Z¹ and Z² each independently represent a polymerizable group.

Furthermore, when the compound of the present invention is a polymer compound having a repeating unit represented by the above formula (A) to (H), (J) or (K), the compound of the present invention can be produced by condensation polymerization of a compound represented by the formula: Z³-A²-Z⁴ corresponding to the repeating unit. Furthermore, in the above formula, Z³ and Z⁴ each independently represent a polymerizable group.

Examples of the polymerizable group include a halogen atom, an alkylsulfonate group, an arylsulfonate group, an arylalkylsulfonate group, a boric acid ester residue, a sulfoniummethyl group, a phosphoniummethyl group, a phosphonatemethyl group, a monohalogenated methyl group, a boric acid residue (—B(OH)₂), a formyl group, a cyano group and a vinyl group.

Examples of the halogen atom serving as a polymerizable group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkylsulfonate group serving as a polymerizable group include a methanesulfonate group, an ethanesulfonate group and a trifluoromethanesulfonate group.

Examples of the arylsulfonate group serving as a polymerizable group include a benzenesulfonate group and a p-toluenesulfonate group.

Examples of the arylalkylsulfonate group serving as a polymerizable group include a benzylsulfonate group.

Examples of the boric acid ester residue serving as a polymerizable group include groups represented by the following formulas:

wherein Me represents a methyl group and Et represents an ethyl group.

Examples of the sulfoniummethyl group serving as a polymerizable group include groups represented by the following formulas: —CH₂S⁺Me₂X′⁻, —CH₂S⁺Ph₂X′⁻ wherein X′ represents a halogen atom and Ph represents a phenyl group.

Examples of the phosphoniummethyl group serving as a polymerizable group include groups represented by the following formula: —CH₂P⁺Ph₃X′⁻ wherein X′ represents a halogen atom.

Examples of the phosphonatemethyl group serving as a polymerizable group include groups represented by the following formula: —CH₂PO(OR′)₂ wherein R′ represents an alkyl group, an aryl group or an arylalkyl group.

Examples of the monohalogenated methyl group serving as a polymerizable group include a methyl fluoride group, a methyl chloride group, a methyl bromide group and a methyl iodide group.

When a zero-valence nickel complex for the Yamamoto coupling reaction or the like is used, examples of the polymerizable group include a halogen atom, an alkylsulfonate group, an arylsulfonate group and an arylalkylsulfonate group. When a nickel catalyst or a palladium catalyst for the Suzuki coupling reaction or the like is used, examples thereof include an alkylsulfonate group, a halogen atom, a boric acid ester residue and boric acid residue.

When the compound of the present invention is a polymer compound, the compound of the present invention is produced by using a compound having a plurality of polymerizable groups serving as a monomer, if necessary, dissolved in an organic solvent, and using, for example, an alkali and an appropriate catalyst and at a temperature of not less than the melting point of the organic solvent and not more than the boiling point. Examples of the method that can be used include methods described in “Organic Reactions”, Vol. 14, pages 270-490, John Wiley & Sons, Inc., 1965, “Organic Syntheses”, Collective Volume VI, pages 407-411, John Wiley & Sons, Inc., 1988, Chem. Rev., Vol. 95, page 2457 (1995), J. Organomet. Chem., Vol. 576, page 147 (1999), Makromol. Chem., Macromol. Symp.), Vol. 12, page 229 (1987).

When the compound of the present invention is a polymer compound, in the method for producing the compound of the present invention, a known condensation reaction can be used depending upon the type of polymerizable group. Examples thereof include a method of polymerizing the corresponding monomer by the Suzuki coupling reaction, a method of polymerizing by the Grignard reaction, a method of polymerizing by an Ni(0) complex, a method of polymerizing by an oxidizing agent such as FeCl₃, a method of performing oxidative polymerization in an electrochemical manner and a method by decomposing an intermediate polymer having an appropriate leaving group.

Of these, a method of polymerizing by the Suzuki coupling reaction, a method of polymerizing by the Grignard reaction, and a method of polymerizing by a nickel zero-valence complex are preferable in view of structural control.

Of the methods for producing the compound of the present invention, a production method using a polymerizable group selected from a halogen atom, an alkylsulfonate group, an arylsulfonate group and an arylalkylsulfonate group through and performed by a condensation polymerization in the presence of a nickel zero-valence complex is preferable.

Examples of a compound serving as a raw material for the compound of the present invention include a dihalogenated compound, a bis(alkylsulfonate) compound, a bis(arylsulfonate) compound, a bis(arylalkyl sulfonate) compound, a halogen-alkylsulfonate compound, a halogen-arylsulfonate compound, a halogen-arylalkylsulfonate compound, an alkylsulfonate-arylsulfonate compound, an alkylsulfonate-arylalkylsulfonate compound and an arylsulfonate-arylalkylsulfonate compound. Furthermore, when a polymer compound controlled in sequence is produced, examples of the compound that may be preferably used include a halogen-alkylsulfonate compound, a halogen-arylsulfonate compound, a halogen-arylalkylsulfonate compound, an alkylsulfonate-arylsulfonate compound, an alkylsulfonate-arylalkylsulfonate compound and an arylsulfonate-arylalkylsulfonate compound.

When the compound of the present invention is a polymer compound, a method for producing the compound of the present invention is, in view of easiness of synthesizing the polymer compound, preferably a production method using a polymerizable group, which is selected from a halogen atom, an alkylsulfonate group, an arylsulfonate group, an arylalkylsulfonate group, a boric acid residue and a boric acid ester residue such that the ratio of the total mole number (J) of the halogen atom, alkylsulfonate group, arylsulfonate group and arylalkylsulfonate group contained in the whole raw-material compound and the total mole number (K) of boric acid residue and boric acid ester residue becomes substantially 1 (usually, K/J is 0.7 to 1.2), and performed by a condensation polymerization method using a nickel catalyst or a palladium catalyst.

Examples of a combination of compounds serving as raw materials (more specifically, a compound represented by the above formula: Y¹-A¹-Y² and a compound represented by the above formula: Y³-A²-Y⁴) include a combination of a dihalogenated compound, a bis(alkylsulfonate) compound, a bis(arylsulfonate) compound or a bis(arylalkylsulfonate) compound and a diboric acid compound or diboric acid ester compound.

Furthermore, when a polymer compound controlled in sequence is produced, examples of the compound that may be preferably used include a halogen-boric acid compound, a halogen-boric acid ester compound, an alkylsulfonate-boric acid compound, an alkylsulfonate-boric acid ester compound, an arylsulfonate-boric acid compound, an arylsulfonate-boric acid ester compound, an arylalkylsulfonate-boric acid compound, an arylalkylsulfonate-boric acid compound and an arylalkylsulfonate-boric acid ester compound.

The organic solvent to be used in the condensation polymerization is preferably treated in advance sufficiently in a deoxidization process and a dehydration process in order to suppress a side reaction. However, this is not applied to the case where a reaction is performed in a two-phase system with water like the Suzuki coupling reaction.

Examples of the organic solvent to be used in the condensation polymerization include saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane; unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene; halogenated saturated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane; halogenated unsaturated hydrocarbon such as chlorobenzene, dichlorobenzene and trichlorobenzene; alcohols such as methanol, ethanol, propanol, isopropanol, butanol and t-butyl alcohol; carboxylic acids such as formic acid, acetic acid and propionic acid; ethers such as dimethyl ether, diethyl ether, methyl-t-butyl ether, tetrahydrofuran, tetrahydropyrane and dioxane; amines such as trimethylamine, triethylamine, N,N,N′,N′-tetramethylethylenediamine and pyridine; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide and N-methylmorpholineoxide. Ethers are preferable and tetrahydrofuran and diethylether are particularly preferable. These organic solvents may be used alone or in combination with two or more types.

In the condensation polymerization, an alkali and a suitable catalyst may be appropriately added to facilitate the reaction. The alkali and catalyst are preferably dissolved sufficiently in the solvent to be used in the reaction. To add the alkali or catalyst, a solution of the alkali or catalyst is added slowly while a reaction solution is stirred under the atmosphere of an inert gas such as argon and nitrogen, or conversely, a reaction solution may be slowly added to a solution of the alkali or catalyst.

When the compound of the present invention is used for producing a light-emitting device, the purity of the compound influences performance of the light-emitting device such as a luminescence property. Therefore, a raw material compound before subjected to polymerization is preferably purified by a method such as distillation, sublimation or recrystallization and thereafter subjected to polymerization. Further after the polymerization, purification such as purification by reprecipitation and fractionation by chromatography is preferably applied.

When the compound of the present invention is produced, a compound represented by the above formula (X) is preferably used.

In the above formula (X), an arylene group, a divalent heterocyclic group and a divalent aromatic amine group represented by Ar¹, a phenylene group represented by J¹, an alkylene group represented by J², and a halogen atom represented by X¹ and X² are the same as defined above.

As the halogen atom represented by X¹ and X², in view of easiness of synthesizing the compound to be obtained, a bromine atom and an iodine atom are preferable and a bromine atom is more preferable.

As the compound represented by the above formula (X), the compounds represented by the following formulas are mentioned.

Furthermore, the compound represented by the above formula (X) may be produced by any method. For example, the compound can be produced by a method including reacting a compound represented by the above formula (XI) and a compound represented by the above formula (XII) in a base.

As the base to be used in the above reaction, an inorganic base such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide or an organic base such as triethylamine is added in an amount of 1 equivalent or more relative to the above formula (XI) and preferably 1 to 20 equivalents and subjected to the reaction.

In the above reaction, usually, a solvent is used. Examples of the solvent include N,N-dimethylformamide, dimethylsulfoxide, toluene, dimethoxyethane and tetrahydrofuran.

The reaction temperature of the above reaction is usually 0° C. to the boiling point of the solvent and preferably 50 to 150° C. Furthermore, the reaction time of the above reaction is 0.5 to 100 hours.

<Composition>

The composition of the present invention is a composition comprising the compound of the present invention. For example, a composition comprising at least one selected from the group consisting of a hole transport material, an electron transport material and a light-emitting material, and a polymer compound as mentioned above, is mentioned.

Furthermore, the composition of the present invention can be rendered also to be a liquid composition further by adding a solvent thereto. More specifically, the liquid composition of the present invention is a liquid composition containing a polymer compound as mentioned above and a solvent. Hereinafter, the composition of the present invention and the liquid composition of the present invention are collectively referred to as “the liquid composition”.

The liquid composition of the present invention is useful for producing a light-emitting device such as a light-emitting device and an organic transistor. In the specification, “the liquid composition” refers to a composition which is present as a liquid state when a device is produced, and typically refers to a composition present in a liquid state at normal pressure (more specifically, 1 atm) and at 25° C. Furthermore, the liquid composition is sometimes generally called as ink, an ink composition and solution, etc.

The liquid composition of the present invention may contain, other than a polymer compound as mentioned above, a low molecular light-emitting material, a hole transport material, an electron transport material, a stabilizer, additives for controlling viscosity and/or surface tension and an antioxidant, etc. These optional components each may be used alone or in combination with two or more types.

Examples of the low molecular light-emitting material include a naphthalene derivative, anthracene, an anthracene derivative, perylene, a perylene derivative, a polymethine-based pigment, a xanthene-based pigment, a coumarin-based pigment, a cyanine-based pigment, a metal complex containing a metal complex of an 8-hydroxyquinoline as a ligand, a metal complex containing a metal complex of an 8-hydroxyquinoline derivative as a ligand, other fluorescent metal complexes, an aromatic amine, tetraphenylcyclopentadiene, a tetraphenylcyclopentadiene derivative, tetraphenylcyclobutadiene, a tetraphenylcyclobutadiene derivative, fluorescent materials such as stilbene-, a silicon-containing aromatic-, oxazole-, furoxan-, thiazole-, tetraarylmethane-, thiadiazole-, pyrazole-, metacyclophane- and acetylene-based low molecular compounds. In addition, materials described in JP 57-51781 A and JP 59-194393 A etc. are included.

Examples of the hole transport material include polyvinyl carbazole and a derivative thereof, polysilane and a derivative thereof, a polysiloxane derivative having an aromatic amine in the side chain or main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, polyaniline and a derivative thereof, polythiophene and a derivative thereof, polypyrrole and a derivative thereof, poly(p-phenylenevinylene) and a derivative thereof, and poly(2,5-thienylenevinylene) and a derivative thereof.

Examples of the electron transport material include, an oxadiazole derivative, anthraquinodimethane and a derivative thereof, benzoquinone and a derivative thereof, naphthoquinone and a derivative thereof, anthraquinone and a derivative thereof, tetracyanoanthraquinodimethane and a derivative thereof, a fluorenone derivative, diphenyldicyanoethylene and a derivative thereof, a diphenoquinone derivative, metal complexes of 8-hydroxyquinoline and a derivative thereof; polyquinoline and a derivative thereof, polyquinoxaline and a derivative thereof, and polyfluorene and a derivative thereof.

Examples of the stabilizer include a phenolic antioxidant and a phosphoric antioxidant.

As additives for controlling viscosity and/or surface tension, a high molecular-weight compound (thickening agent) and a poor solvent for increasing viscosity, a low molecular-weight compound for decreasing viscosity and a surfactant for decreasing surface tension etc. may be used in appropriate combination.

As the high molecular-weight compound, any high molecular-weight compound may be used as long as it does not inhibit light emission and charge transport, and it is usually a soluble compound in the solvent for a liquid composition. As the high molecular-weight compound, a high molecular weight polystyrene and a high molecular weight polymethylmethacrylate, etc. can be used. The polystyrene-equivalent weight average molecular weight of the high molecular-weight compound is preferably 500,000 or more and more preferably 1,000,000 or more. Furthermore, a poor solvent can be used as a thickening agent.

As the antioxidant, any antioxidant may be used as long as it does not inhibit light emission and charge transport, and if a composition contains a solvent, the antioxidant soluble in the solvent is usually used. Examples of the antioxidant include a phenolic antioxidant and a phosphoric antioxidant. Storage stability of the polymer compound and the solvent can be improved by use of the antioxidant.

When the liquid composition of the present invention contains a hole transport material, the ratio of the hole transport material in the liquid composition is usually 1 to 80 wt % and preferably 5 to 60 wt %. Furthermore, when the liquid composition of the present invention contains an electron transport material, the ratio of the electron transport material in the liquid composition is usually 1 to 80 wt % and preferably 5 to 60 wt %.

When a film is formed by using the liquid composition in producing a light-emitting device, after the liquid composition is applied, all that should be done is just removing a solvent by drying. In addition, when a charge transport material and a light-emitting material are added, the same procedure can be applied. Therefore, the liquid composition is extremely favorable in view of production. Note that drying may be performed in a warm state of about 50 to 150° C. or under reduced pressure of about 10⁻³ Pa.

In forming a film using the liquid composition, a coating method can be used such as a spin coating method, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a slit coating method, a cap coating method, a capillary coating method, a spray coating method, a screen printing method, a flexo printing method, an offset printing method, an inkjet printing method and a nozzle coating method.

The ratio of a solvent in the liquid composition is usually 1 to 99.9 wt % relative to the total weight of the liquid composition, preferably 60 to 99.9 wt % and more preferably, 90 to 99.8 wt %. The viscosity of the liquid composition, which varies depending upon the printing method, is preferably 0.5 to 500 mPa·s at 25° C. In the case where the liquid composition passes through an ejection apparatus as in the case of inkjet printing method etc., viscosity is preferably 0.5 to 20 mPa·s at 25° C. to prevent clogging during ejection and bending of sprayed liquid composition.

As the solvent contained in the liquid composition, a solvent capable of dissolving or dispersing components of the liquid composition except the solvent is preferable. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichloro benzene; ether solvents such as tetrahydrofuran and dioxane; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene and mesitylene; aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; ketone solvents such as acetone, methylethylketone and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, methyl benzoate and ethyl cellosolve acetate; polyhydric alcohols and a derivative thereof such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylether, ethylene glycol monomethylether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethylether, glycerin and 1,2-hexanediol; alcohol solvents such as methanol, ethanol, propanol, isopropanol and cyclohexanole; sulfoxide solvents such as dimethylsulfoxide; and amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide. Furthermore, these solvents may be used alone or in combination of more than one types. Of the solvents, one or more organic solvents having a structure having at least one benzene ring and having a melting point of 0° C. or less and a boiling point of 100° C. or more is preferably contained in view of viscosity and film forming property etc. As the type of solvent, in view of solubility of the components of the liquid composition except the solvent in an organic solvent, uniformity of the film formed and viscosity property, etc., an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an ester solvent and a ketone solvent are preferable. Preferable examples thereof include toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, mesitylene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, s-butylbenzene, anisole, ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexyl benzene, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methylbenzoate, 2-propylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone and dicyclohexyl ketone. More preferably, at least one of the solvents including xylene, anisole, mesitylene, cyclohexylbenzene and bicyclohexylmethylbenzoate, is contained.

The number of types of solvents contained in the liquid composition, in view of film forming property and device characteristic, is preferably 2 or more, more preferably 2 to 3 and particularly preferably 2.

When 2 types of solvents are contained in the liquid composition, one of the solvents may be in a solid state at 25° C. In view of film forming property, it is preferable that one of the solvents has a boiling point of 180° C. or more and the other solvent has a boiling point of less than 180° C. It is more preferable that one of the solvents has a boiling point of 200° C. or more and the other solvent has a boiling point of less than 180° C. Furthermore, in view of viscosity, 0.2 wt % or more of the components of the liquid composition from which a solvent is removed is preferably dissolved in the solvent at 60° C. In one of the two types of solvents, 0.2 wt % or more of the components of the liquid composition from which a solvent is removed is preferably dissolved at 25° C.

When three types of solvents are contained in the liquid composition, one to two types of solvents may be in a state of solid at 25° C. In view of film forming property, it is preferable that at least one of the three types of solvents has a boiling point of 180° C. or more and at least one of the solvents has a boiling point of less than 180° C. It is more preferable that at least one of the three types of solvents has a boiling point of 200° C. or more and 300° C. or less and at least one of the solvents has a boiling point of less than 180° C. In view of viscosity, in two types of the three types of solvents, 0.2 wt % or more of the components of the liquid composition from which a solvent is removed is preferably dissolved at 60° C. In one of the three types of solvents, 0.2 wt % or more of the components of the liquid composition from which a solvent is removed is preferably dissolved at 25° C.

When two or more types of solvents are contained in the liquid composition, in view of viscosity and film forming property, the content of the solvent having the highest boiling point is preferably 40 to 90 wt % of the total solvents contained in the liquid composition and more preferably 50 to 90 wt % and further preferably 65 to 85 wt %.

<Film>

A film of the present invention will be described. The film is formed of a polymer compound as mentioned above. As the type of film, a luminous film, a conductive film and an organic semiconductor film, etc. are mentioned.

Furthermore, a film according to a second aspect of the present invention is formed by crosslinking of the polymer compound. The film is usually hardened by crosslinking caused by an external stimulus such as heat or light.

The heat for hardening a film is not particularly limited; however, it generally falls within the range of room temperature to 300° C. The upper limit thereof is, in view of easiness of forming a film, preferably 250° C., further preferably 190° C. and most preferably 170° C. Furthermore, the lower limit is, in view of stability of a film at room temperature, preferably 50° C., further preferably 70° C. and most preferably 100° C.

The light for hardening a film is not particularly limited; however, generally UV light, near ultra violet light and visible light are used, and UV light and near ultra violet light are preferable.

When the film of the present invention is hardened, the hardening rate can be controlled depending upon the temperature, time or light exposure wavelength and exposure time.

The luminous film, in view of brightness of a device and emission voltage etc., preferably has, an emission quantum yield of 50% or more, more preferably 60% or more and further preferably 70% or more.

A conductive film preferably has a surface resistance of 1 KΩ/□ or less. The electric conductivity of the film can be improved by doping a Lewis acid and an ionic compound, etc. thereto. The surface resistance is more preferably 100Ω/□ or less and further preferably, 10Ω/□ or less.

In an organic semiconductor film, a larger one of an electron mobility and a hole mobility is preferably 10⁻⁵ cm²/V/second or more, more preferably 10⁻³ cm²/V/second or more and further preferably 10⁻¹ cm²/V/second or more. Furthermore, an organic transistor can be produced by using an organic semiconductor film. Specifically, an organic transistor can be obtained by forming an organic semiconductor film on an Si substrate having an insulating film such as SiO₂ and a gate electrode formed thereon, and forming a source electrode and a drain electrode of Au, etc.

<Organic Transistor>

The organic transistor of the present invention is an organic transistor containing a compound as mentioned above. Hereinafter, an embodiment of the organic transistor, that is, a field effect transistor, will be described.

The compound of the present invention can be suitably used as a material for field effect transistor, in particular, as a material for an active layer. As the structure of the field effect transistor, it is usually satisfactory if a source electrode and a drain electrode are provided in contact with an active layer formed of the compound of the present invention and a gate electrode is provided so as to sandwich an insulating layer in contact with the active layer.

The field effect transistor is usually formed on a supporting substrate. As the supporting substrate, a glass substrate, a flexible film substrate as well as a plastic substrate can be used.

A field effect transistor can be produced by a known method, for example, a method described in JP 5-110069 A.

When an active layer is formed, use of a compound soluble in an organic solvent is favorable and preferable in view of production. In forming a film from a solution prepared by dissolving a compound soluble in an organic solvent in a solvent, a spin coating method, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a slit coating method, a cap coating method, a capillary coating method, a spray coating method, a screen printing method, a flexo printing method, an offset printing method, an inkjet printing method and a nozzle coating method can be used.

After the field effect transistor is produced and preferably encapsulated to form an encapsulated field effect transistor. By virtue of this, the field effect transistor can be blocked from the air and suppressed from deterioration of characteristics thereof.

As the encapsulating method, e.g., a method of covering with a UV rays (UV) curable resin, a thermosetting resin and an inorganic SiONx film, etc. and a method of joining glass plates and films with a UV rays (UV) curable resin or a thermosetting resin are mentioned. To effectively block a field effect transistor from the air, it is preferred to perform steps from production thereof to encapsulation without being exposed to the air (for example, in a dry nitrogen atmosphere or in vacuum).

<Organic Photoelectric Transducer>

An organic photoelectric transducer of the present invention (for example, solar battery) is an organic photoelectric transducer containing the aforementioned compound.

The compound of the present invention can be preferably used as a material for an organic photoelectric transducer, in particular, as an organic semiconductor layer of a Schottky barrier type device using the interface between an organic semiconductor and a metal, and furthermore, as an organic semiconductor layer of a pn-heterojunction type device using the interface between an organic semiconductor and an inorganic semiconductor or the interface between organic semiconductors.

Furthermore, the compound of the present invention can be preferably used as an electron donating compound and an electron receptor compound in a bulk heterojunction device increased in donor/acceptor contact area, furthermore, an organic photoelectric transducer using a polymer/low molecular complex system, for example, as an electron donating conjugated compound (diffusion support) of a bulk heterojunction organic photoelectric transducer having a fullerene derivative dispersed therein as an electron receptor.

As a structure of an organic photoelectric transducer, for example, in a pn-heterojunction device, it is satisfactory if a p-type semiconductor layer is formed on ITO, further an n-type semiconductor layer is laminated thereon, and an ohm electrode is provided thereon.

The organic photoelectric transducer is usually formed on a supporting substrate. As the supporting substrate, a glass substrate, a flexible film substrate as well as a plastic substrate can be used.

An organic photoelectric transducer can be produced by a known method, for example, a method described in Synth. Met., 102, 982 (1999) and a method described in Science, 270, 1789 (1995).

<Light-Emitting Device>

Next, a light-emitting device of the present invention will be described.

The light-emitting device of the present invention is a light-emitting device having electrodes comprising an anode and a cathode, and an organic layer provided between the electrodes and containing the compound of the present invention, preferably a light-emitting device having an organic layer serving as a light-emitting layer or a charge transport layer. Examples of the light-emitting device of the present invention include (1) an light-emitting device having an electron transport layer provided between a cathode and a light-emitting layer, (2) a light-emitting device having a hole transport layer provided between an anode and a light-emitting layer and (3) a light-emitting device having an electron transport layer provided between a cathode and a light-emitting layer and having a hole transport layer provided between an anode and the light-emitting layer.

More specifically, the following structures a) to d) are mentioned.

a) anode/light-emitting layer/cathode

b) anode/hole transport layer/light-emitting layer/cathode

c) anode/light-emitting layer/electron transport layer/cathode

d) anode/hole transport layer/light-emitting layer/electron transport layer/cathode

(wherein symbol “/” indicates that individual layers are laminated in adjacent to each other. The same is applied in the following)

The light-emitting layer is a layer having a function of emitting light. The hole transport layer is a layer having a function of transporting holes, The electron transport layer is a layer having a function of transporting electrons. Note that the electron transport layer and the hole transport layer are collectively called a charge transport layer. As the light-emitting layer, hole transport layer and electron transport layer each may consists of two layers or more. Furthermore, the hole transport layer provided in adjacent to a light-emitting layer is sometimes called as an interlayer.

As a method for forming a light-emitting layer, a method of forming a film from a solution is mentioned. In forming a film from a solution, a spin coating method, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a slit coating method, a cap coating method, a capillary coating method, a spray coating method, a screen printing method, a flexo printing method, an offset printing method, an inkjet printing method and a nozzle coating method can be used. Note that the formation of a film from a solution is useful for forming films of a hole transport layer and an electron transport layer (described later).

When a film is formed from a solution by using the compound of the present invention in producing a light-emitting device, all that should be done after the solution is applied, is just removing a solvent by drying. Furthermore, even in the case where a charge transport material and a light-emitting material are added, the same procedure can be applied and thus favorable in production.

The film thickness of a light-emitting layer, which may be selected such that appropriate driving voltage and luminous efficiency values are obtained, is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm and further preferably 5 nm to 200 nm.

In the light-emitting device of the present invention, a light-emitting material except the aforementioned compound may be used in combination in a light-emitting layer. Furthermore, in the light-emitting device of the present invention, a light-emitting layer containing a light-emitting material except the aforementioned compound and a light-emitting layer containing the aforementioned compound may be laminated.

Examples of a light-emitting material except the aforementioned compound include low molecular compounds such as a naphthalene derivative, anthracene and a derivative thereof, perylene and a derivative thereof, pigments including a polymethine-based pigment, a xanthene-based pigment, a coumarin-based pigment and a cyanine-based pigment, a metal complex of 8-hydroxyquinoline and a derivative thereof, an aromatic amine, tetraphenylcyclopentadiene and a derivative thereof and tetraphenylbutadiene and a derivative thereof. In addition, the compounds described in JP 57-51781 A and JP 59-194393 A, etc. may be mentioned.

When the light-emitting device of the present invention has a hole transport layer, the hole transport material to be used herein is the same as the hole transport material described in the section of the liquid composition; however, preferable examples thereof include polymer hole transport materials such as polyvinylcarbazole and a derivative thereof, polysilane and a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in the side chain or main chain, polyaniline and a derivative thereof, polythiophene and a derivative thereof, poly(p-phenylenevinylene) and a derivative thereof, poly(2,5-thenylenevinylene) and a derivative thereof. More preferable examples thereof include, polyvinyl carbazole and a derivative thereof, polysilane and a derivative thereof and a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low molecular hole transport material, it is preferably dispersed in a polymer binder and put in use.

As a method for forming a hole transport layer, in the case of a low molecular hole transport material, a method for forming a film from a solution containing a polymer binder mixed therein is mentioned. Furthermore, in the case of a high-molecular hole transport material, a method for forming a film from a solution is mentioned.

As the polymer binder to be mixed, a polymer binder that does not significantly inhibit charge transport is preferable and a polymer binder that does not significantly absorb visible light is suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethylacrylate, polymethylmethacrylate, polystyrene, polyvinyl chloride and polysiloxane.

The film thickness of the hole transport layer, which may be selected such that appropriate driving voltage and luminous efficiency values are obtained, is for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and further preferably 5 nm to 200 nm.

When the light-emitting device of the present invention has an electron transport layer, the electron transport material to be used is the same as the electron transport material as described in the section of the liquid composition; however, preferable examples thereof include an oxadiazole derivative, benzoquinone and a derivative thereof, anthraquinone and a derivative thereof, a metal complex of 8-hydroxy quinoline and a derivative thereof, polyquinoline and a derivative thereof, polyquinoxaline and a derivative thereof and polyfluorene and a derivative thereof; and more preferable examples thereof include 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, benzoquinone, anthraquinone, tris(8-quinolinol)aluminum and polyquinoline.

As a method for forming a film of the electron transport layer method, in the case of a low-molecular electron transport material, a vapor deposition method for forming a film from a powder, and a method for forming a film from a solution or a molten state are mentioned; in the case of a high-molecular electron transport material, a method for forming a film from a solution or a molten state is mentioned. When a film is formed from a solution or a molten state, a polymer binder may be used in combination.

As the polymer binder to be added, a polymer binder that does not significantly inhibit charge transport is preferable, and a polymer binder that does not significantly absorb visible light is suitably used. Examples of the polymer binder include poly(N-vinylcarbazole), polyaniline and a derivative thereof, polythiophene and a derivative thereof, poly(p-phenylenevinylene) and a derivative thereof, poly(2,5-thienylenevinylene) and a derivative thereof, polycarbonate, polyacrylate, polymethylacrylate, polymethylmethacrylate, polystyrene, polyvinyl chloride and polysiloxane.

The film thickness of the electron transport layer may be selected such that appropriate driving voltage and luminous efficiency values are obtained, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and further preferably 5 nm to 200 nm.

Furthermore, of the charge transport layers provided in adjacent to an electrode, a charge transport layer having a function of improving an efficiency of charge injection from an electrode and having an effect of reducing the driving voltage of a device is sometimes particularly called a charge injection layer (hole injection layer, electron injection layer).

Furthermore, to improve adhesion with an electrode and to improve injection of charge from an electrode, the charge injection layer or an insulating layer may be provided in adjacent to the electrode. Moreover, to improve adhesion at the interface and prevent contamination, etc., a thin buffer layer may be inserted in the interface between a charge transport layer and a light-emitting layer.

The order and number of layers to be laminated and the thickness of each layer may be appropriately selected in consideration of luminous efficiency and device life.

In the present invention, as a light-emitting device having a charge injection layer provided therein, a light-emitting device having a charge injection layer provided in adjacent to a cathode and a light-emitting device having a charge injection layer provided in adjacent to an anode are mentioned.

Specific examples thereof include the following structures e) to p).

e) anode/charge injection layer/light-emitting layer/cathode,

f) anode/light-emitting layer/charge injection layer/cathode,

g) anode/charge injection layer/light-emitting layer/charge injection layer/cathode,

h) anode/charge injection layer/hole transport layer/light-emitting layer/cathode,

i) anode/hole transport layer/light-emitting layer/charge injection layer/cathode,

j) anode/charge injection layer/hole transport layer/light-emitting layer/charge injection layer/cathode,

k) anode/charge injection layer/light-emitting layer/charge transport layer/cathode,

l) anode/light-emitting layer/electron transport layer/charge injection layer/cathode,

m) anode/charge injection layer/light-emitting layer/electron transport layer/charge injection layer/cathode,

n) anode/charge injection layer/hole transport layer/light-emitting layer/charge transport layer/cathode,

o) anode/hole transport layer/light-emitting layer/electron transport layer/charge injection layer/cathode,

p) anode/charge injection layer/hole transport layer/light-emitting layer/electron transport layer/charge injection layer/cathode.

Examples of the charge injection layer include a layer containing a conductive polymer; a layer provided between an anode and a hole transport layer and containing a material having an intermediate ionization potential value between an anode material and a hole transport material contained in the hole transport layer, and a layer provided between a cathode and an electron transport layer and containing a material having an intermediate affinity value for electron between a cathode material and an electron transport material contained in the electron transport layer.

When the charge injection layer is a layer containing a conductive polymer, the electric conductivity of the conductive polymer is preferably 10⁻⁵ to 10³ S/cm. To reduce current leakage between emission pixels, the electric conductivity is more preferably 10⁻⁵ to 10² S/cm and further preferably 10⁻⁵ to 10¹ S/cm. Usually, to control the electric conductivity of the conductive polymer to be 10⁻⁵ to 10³ S/cm, an appropriately amount of ion is doped in the conductive polymer.

Type of ion to be doped is anion in the case of a hole injection layer and cation in the case of an electron injection layer. Examples of the anion include polystyrene sulfonate ion, alkyl benzene sulfonate ion and camphor sulfonate ion. Examples of the cations include a lithium ion, a sodium ion, a potassium ion and a tetrabutylammonium ion.

The film thickness of the charge injection layer is, for example, 1 nm to 100 nm and preferably 2 nm to 50 nm.

Examples of the material to be used for the charge injection layer include polyaniline and a derivative thereof, polythiophene and a derivative thereof, polypyrrole and a derivative thereof, polyphenylenevinylene and a derivative thereof, polythienylenevinylene and a derivative thereof, polyquinoline and a derivative thereof, polyquinoxaline and a derivative thereof, a conductive polymer such as a polymer having an aromatic amine structure in the main chain or side chain, metal phthalocyanine (copper phthalocyanine, etc.) and carbon.

The insulating layer is a layer having a function of facilitating charge injection. The average thickness of the insulating layer is, usually, 0.1 to 20 nm, preferably 0.5 to 10 nm and more preferably 1 to 5 nm. Examples of a material for the insulating layer include a metal fluoride, a metal oxide and an organic insulating material. As a light-emitting device having an insulating layer provided therein, a light-emitting device having an insulating layer provided in adjacent to a cathode and a light-emitting device having an insulating layer provided in adjacent to an anode are mentioned.

Specific examples thereof include the following structures q) to ab).

q) anode/insulating layer/light-emitting layer/cathode,

r) anode/light-emitting layer/insulating layer/cathode,

s) anode/insulating layer/light-emitting layer/insulating layer/cathode,

t) anode/insulating layer/hole transport layer/light-emitting layer/cathode,

u) anode/hole transport layer/light-emitting layer/insulating layer/cathode,

v) anode/insulating layer/hole transport layer/light-emitting layer/insulating layer/cathode,

w) anode/insulating layer/light-emitting layer/electron transport layer/cathode,

x) anode/light-emitting layer/electron transport layer/insulating layer/cathode,

y) anode/insulating layer/light-emitting layer/electron transport layer/insulating layer/cathode,

z) anode/insulating layer/hole transport layer/light-emitting layer/electron transport layer/cathode,

aa) anode/hole transport layer/light-emitting layer/electron transport layer/insulating layer/cathode,

ab) anode/insulating layer/hole transport layer/light-emitting layer/electron transport layer/insulating layer/cathode.

As the substrate for forming the light-emitting device of the present invention, any substrate may be used as long as it remains unchanged when an electrode is formed and an organic material layer is formed. Examples of the substrates include glass, plastic, a polymer film and silicon substrates. In the case of an opaque substrate, the opposite electrode is preferably transparent or semitransparent.

In the present invention, at least one of the electrodes comprising an anode and a cathode is usually transparent or semitransparent and preferably the anode is transparent or semitransparent.

As a material for the anode, a conductive metal oxide film and a semitransparent metal film, etc. are used. More specifically, a film (NESA, etc.) formed of conductive glass using indium oxide, zinc oxide, tin oxide and a complex thereof, that is, indium/tin/oxide (ITO) and indium/zinc/oxide, etc. gold, platinum, silver and copper, etc. are used, and ITO, indium/zinc/oxide and tin oxide are preferable. Examples of a forming method include a vapor deposition method, a sputtering method, an ion-plating method and a plating method. Furthermore, as the anode, a transparent conducting film of an organic substance such as polyaniline and a derivative thereof and polythiophene and a derivative thereof.

The film thickness of the anode is, in view of light permeability/electric conductivity, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm and further preferably 50 nm to 500 nm.

Furthermore, to facilitate charge injection, a layer formed of e.g., a phthalocyanine derivative, a conductive polymer or carbon, or a layer formed of e.g., a metal oxide, a metal fluoride or an organic insulating material may be provided on the anode.

As a material for the cathode, a material having a small work function is preferable. Examples thereof that are used include a metal such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium and ytterbium; an alloy of two or more types of them or an alloy of one or more of them with one or more of, e.g., gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin; and graphite or an graphite intercalation compound. Examples of the alloy include a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy and a calcium-aluminum alloy. The cathode may have a laminate structure of 2 layers or more.

The film thickness of the cathode is, in view of electric conductivity and durability, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and further preferably 50 nm to 500 nm.

As a method for forming the cathode, a vapor deposition method, a sputtering method and a laminate method in which a metal film is attached by thermo compression bonding are used. Furthermore, between the cathode and the organic material layer, a layer formed of a conductive polymer or a layer formed of a metal oxide, a metal fluoride, an organic insulating material or the like may be provided. Alternatively after the cathode is formed, a protecting layer for protecting the light-emitting device may be attached. To use the light-emitting device stably for a long time, a protecting layer and/or a protecting cover is preferably attached to protect the device from the outside.

As the protecting layer, a resin, a metal oxide, a metal fluoride and a metal borate, etc. can be used. Furthermore, as the protecting cover, a glass plate, a plastic plate having a surface treated to lower water permeability, and the like can be used. A method in which the cover is allowed to adhere airtight to a device substrate with a thermosetting resin or a light curable resin can be preferably used. If a spacer is used to keep a space, the device is easily protected from damage. If an inert gas such as nitrogen and argon is supplied to the space, the cathode can be prevented from being oxidized. Furthermore, if a desiccating agent such as barium oxide is placed in the space, the device is easily prevented from damage with a moisture content introduced by adsorption in a production step. At least one of these measures is preferably employed.

The light-emitting device of the present invention can be used in displays such as a surface light source, a segment display, a dot matrix display, a liquid crystal display (for example, a backlight) and a flat panel feris play.

To obtain a planer emission by using the light-emitting device of the present invention, a planar anode and cathode are arranged so as to overlap them. Furthermore, to obtain patterned emission of light, there are a method of placing a mask having a patterned window in the surface of the surface light-emitting device, a method of forming an extremely thick organic material layer in a non light-emitting section such that light is not substantially emitted, and a method of forming a patterned electrode as either one of an anode and cathode or both electrodes. Patterns are formed by any one of these methods and electrodes are arranged so as to independently turn ON/OFF. In this manner, a segment-type display device capable of displaying numeric characters and letters, and simple symbols, etc. can be obtained. Furthermore, to obtain a dot matrix device, an anode and a cathode are formed in the form of stripe and arranged so as to cross perpendicularly. A partial color display and multi-color display can be realized by a method of distinctively applying a plurality of types of light-emitting materials different in luminous color and a method of using a color filter or a fluorescence conversion filter. A dot matrix device can be passively driven or may be actively driven in combination with TFT, etc. These display devices can be used as displays for computers, televisions, mobile terminals, mobile phones, car-navigation and view finders of video cameras, etc.

Furthermore, the surface light-emitting device is usually an autonomous light-emitting thin device and can be preferably used as a surface light source for a backlight of a liquid crystal display or surface illumination light source. For example, as the illumination light source, light emission such as white light emission, red light emission and green light emission or blue light emission are mentioned. Furthermore, if a flexible substrate is used, the light-emitting device can be used also as a curved-surface light source and a curved-surface display device.

EXAMPLES

Examples will be shown below to describe the present invention more specifically; however, the present invention is not limited to these.

Synthesis Example 1 Synthesis of Compound M-1

Under an argon atmosphere, divinylcarbinol (25.24 g), triethyl orthoacetate (340 g) and propionic acid (0.20 g) were blended and warmed to 130° C. for 4 hours while removing ethanol by use of Dean-Stark. After completion of the reaction, the resultant reaction solution was cooled. To the reaction solution, hexane (300 ml) and ion-exchanged water (300 ml) were added, and stirred at 60° C. for 3 hours. After layers were separated, an organic layer was washed with ion-exchanged water (300 ml×3 times) and dried over sodium sulfate. The resultant organic layer was concentrated by passing it through an alumina flush column. To the resultant oil, again, hexane (300 ml), ion-exchanged water (300 ml) and propionic acid (0.20 g) were added and stirred at 60° C. for 8 hours. After layers were separated, an organic layer was washed with ion-exchanged water (300 ml×3 times) and dried over sodium sulfate. The resultant organic layer was concentrated by passing it through an alumina flush column to obtain compound M-1 (28 g) represented by the above formula M-1.

¹H-NMR (270 MHz, CDCl₃): δ=1.25 (t, 3H), 2.07 (q, 2H), 2.41 (m, 4H), 5.05 (dd, 2H), 5.70 (m, 1H), 6.09 (dd, 1H), 6.29 (m, 1H) ppm.

Synthesis Example 2 Synthesis of Compound M-2

Under an argon atmosphere, compound M-1 (14.65 g) and diethyl ether (770 ml) were blended and cooled to 0° C. Subsequently, to the resultant solution mixture, a 1 M lithium aluminum hydride ether solution (50 ml) was added dropwise for one hour and stirred for one hour while the temperature was kept at 0° C. To the resultant reaction solution, a 5 wt % aqueous sodium hydroxide solution (100 ml) was slowly added dropwise and quenched. Thereafter, an organic layer was washed with water (100 ml×3 times) and the organic layer was dried over sodium sulfate. The resultant organic layer was concentrated by passing it through an alumina flush column to obtain compound M-2 (8.0 g) represented by the above formula M-2.

¹H-NMR (270 MHz, CDCl₃): δ=1.67 (tt, 2H), 2.13-2.28 (m, 3H), 3.63 (q, 2H), 5.04 (dd, 2H), 5.72 (dd, 1H), 6.07 (dd, 1H), 6.30 (m, 1H) ppm.

Synthesis Example 3 Synthesis of Compound M-3

Under an argon atmosphere, compound M-2 (18.98 g) and dichloromethane (730 ml) were blended and cooled to 0° C. To the resultant solution mixture, triethylamine (58 ml) was added dropwise and then methane sulfonylchloride (24 ml) was added dropwise and stirred for 2 hours while the temperature was kept at 0° C. To the resultant reaction solution, water was added and quenched and thereafter, extraction with ether and dehydration over sodium sulfate were performed to obtain yellow oil (32 g).

Under an argon atmosphere, the yellow oil (32 g), lithium bromide (36 g) and THF (400 ml) were blended and refluxed for 7 hours. The resultant reaction solution was cooled and ion-exchanged water (200 ml) and toluene (500 ml) were added and then, layers were separated. The organic layer was washed with ion-exchanged water (100 ml×5 times) and dried over sodium sulfate. The resultant organic layer was concentrated. After hexane (100 ml) was added, the organic layer was concentrated by passing it through an alumina flush column. The resultant oil was fractionated (3 mmHg, 27° C.) to obtain compound M-3 (15.1 g) represented by the above formula M-3.

¹H-NMR (270 MHz, CDCl₃): δ=1.96 (tt, 2H), 2.22-2.29 (m, 2H), 3.41 (t, 2H), 5.05 (dd, 2H), 5.65 (m, 1H), 6.10 (dd, 1H), 6.30 (m, 1H) ppm.

Example 1 Synthesis of Compound M-4

Under an argon atmosphere, in a 300 mL four-neck flask, compound M-3 (5.29 g), 2,7-dibromofluorene (4.67 g) and DMSO (35 ml) were blended. To the resultant solution mixture, potassium hydroxide (3.43 g) and potassium iodide (0.17 g) mashed in a mortar were added and warmed at 85° C. for 45 minutes. To the resultant solution mixture, ion-exchanged water (50 ml) and ethyl acetate (100 ml) were added and then layers were separated. The organic layer was washed with a saturated saline solution (100 ml×10 times), dried over sodium sulfate and then concentrated. The resultant oil was purified by silica gel column chromatography (developing solvent: hexane) to obtain compound M-4 (4.9 g) represented by the above formula M-4 as a white solid substance.

¹H-NMR (270 MHz, CDCl₃): δ=0.68 (m, 4H), 1.81-1.96 (m, 8H), 4.99 (dd, 4H), 5.44 (m, 2H), 5.89 (dd, 2H), 6.22 (td, 2H), 7.47 (m, 6H) ppm.

MS (APCI-MS: Positive) m/z: 512 ([M]⁺).

Example 2 Synthesis of Compound M-5

Under an argon atmosphere, in a 100 mL four-neck flask, compound M-3 (1.88 g), 2,5-dibromohydroquinone (2.51 g) and ethanol (7 ml) were blended. To the resultant solution mixture, potassium hydroxide (0.97 g) mashed in a mortar was added and warmed at 85° C. for 9 hours. After completion of the reaction, to the resultant reaction solution, ion-exchanged water (20 ml) and ethyl acetate (20 ml) were added and layers were separated. Thereafter, the organic layer was washed with ion-exchanged water (40 ml×3 times), dried over sodium sulfate and then concentrated. The resultant oil was purified by silica gel column chromatography (developing solvent: toluene/hexane=1:1) to obtain compound M-5 (1.3 g) represented by the above formula M-5 as a white solid substance.

¹H-NMR (270 MHz, CDCl₃): δ=1.87-1.96 (m, 4H), 2.28-2.35 (m, 4H), 3.94 (t, 4H), 5.05 (dd, 4H), 5.75 (m, 2H), 6.10 (m, 2H), 6.31 (m, 2H), 7.08 (s, 2H) ppm.

Example 3 Synthesis of Compound M-7

Under an argon atmosphere, in a 100 mL four-neck flask, compound M-3 (1.63 g), compound M-6 (1.63 g) represented by the above formula M-6 and ethanol (7 ml) were blended. To the resultant solution mixture, potassium hydroxide (0.97 g) mashed in a mortar was added and warmed at 60° C. for 40 hours. After completion of the reaction, to the resultant reaction solution, ion-exchanged water (50 ml) and toluene (50 ml) were added. After layers were separated, an organic layer was washed with ion-exchanged water (40 ml×3 times), dried over sodium sulfate and then concentrated. The resultant oil was purified by silica gel column chromatography (developing solvent: toluene/hexane=1:1) to obtain compound M-7 (1.1 g) represented by the above formula M-7 as a white solid substance.

Note that compound M-6 was synthesized with reference to EP1344788.

¹H-NMR (270 MHz, CDCl₃): δ=1.97-2.06 (m, 4H), 2.36-2.43 (m, 4H), 4.10 (t, 4H), 5.04 (dd, 4H), 5.78 (m, 2H), 6.14 (m, 2H), 6.32 (m, 2H), 7.32 (s, 2H), 7.73 (s, 2H) ppm.

Synthesis Example 4 Synthesis of Compound M-8

Under nitrogen gas atmosphere, to a mixture of 2,7-dibromofluorene (75 g, 0.22 mol), hexylbenzene (334 ml) and trifluoromethanesulfonic acid (42 ml) stirred at room temperature, sodium 3-mercaptopropanesulfonate (8.1 g) was added and stirred at 45° C. for 9 hours. The resultant reaction solution was cooled to room temperature and then added to hexane (1 L). Excess hexyl benzene was distilled away by distillation under reduced pressure (105.5° C., 20 hPa), diluted with hexane and then added to methanol. The precipitated 2,7-dibromofluorenone was removed by filtration. The resultant filtrate was concentrated and then diluted with toluene, and isopropyl alcohol was added to precipitate a solid substance. The resultant solid substance was recrystallized from toluene/isopropyl alcohol to obtain compound M-8 (53 g) represented by the above formula M-8 as a white solid substance.

¹H-NMR (270 MHz, CDCl₃): δ=0.88 (t, 3H), 1.20-1.45 (m, 6H), 1.54-1.62 (m, 2H), 2.57 (t, 2H), 4.96 (s, 1H), 6.94 (d, 2H), 7.10 (d, 2H), 7.42 (s, 2H), 7.48 (dd, 2H), 7.60 (d, 2H) ppm.

Example 4 Synthesis of Compound M-9

Under an argon atmosphere, in a 100 mL four-neck flask, compound M-3 (0.96 g), compound M-8 (2.42 g) and dimethylsulfoxide (12 ml) were blended. To the resultant solution mixture, potassium hydroxide (1.2 g) and potassium iodide (0.08 g) mashed in a mortar were added and stirred at room temperature for 5 hours. After completion of the reaction, to the resultant reaction solution, ion-exchanged water (20 ml) and toluene (30 ml) were added. After layers were separated, an organic layer was washed with a saturated saline solution (30 ml×10 times) and dried over sodium sulfate and then concentrated. The resultant oil was purified by silica gel column chromatography (developing solvent: toluene/hexane=1:10) to obtain compound M-9 (2.0 g) represented by the above formula M-9 as colorless oil.

¹H-NMR (270 MHz, CDCl₃): δ=0.75-0.87 (m, 5H), 1.20-1.39 (m, 6H), 1.52-1.56 (m, 2H), 2.00-2.31 (m, 2H), 2.37-2.44 (m, 2H), 2.50-2.56 (t, 2H), 4.92-5.10 (dd, 2H), 5.44-5.53 (td, 1H), 5.89-5.97 (dd, 1H), 6.17-6.30 (td, 1H), 7.00-7.16 (m, 4H), 7.18-7.28 (dd, 2H), 7.47 (d, 2H), 7.55 (d, 2H) ppm.

Example 5 Synthesis of Compound M-11

Under an argon atmosphere, in a 300 mL three-neck flask, compound M-10 (5.1 g), compound M-3 (3.7 g) and dimethylsulfoxide (100 ml) were blended. To this, potassium hydroxide (1.4 g) was added and stirred at room temperature for 6 hours. After completion of the reaction, water (30 ml) was added. After layers were separated, the resultant organic layer was washed with water, then dried over sodium sulfate, and concentrated to dryness. Subsequently, purification was performed by column chromatography using hexane: chloroform (=6:1) as a developing solvent and silica gel as a filler. Recrystallization was performed to obtain compound M-11 represented by the above formula.

Note that compound M-10 was synthesized with reference to U.S. Pat. No. U.S. Pat. No. 5,447,960.

¹H-NMR (270 MHz, CDCl₃); 1.88 (m, 4H), 2.26 (q, 4H)), 3.93 (t, 4H), 5.15-4.95 (m, 4H), 5.76-5.66 (m, 2H), 6.33-6.27 (m, 2H), 6.75 (d, 4H), 7.03 (d, 4H), 7.57-7.43 (m, 6H).

Synthesis Example 5 Synthesis of Compound MM-1

Under an argon atmosphere, in a 500 ml four-neck flask, 2,7-dibromofluorene (22.7 g), 5-bromo-1-octene (21.9 g), potassium hydroxide (16.7 g), potassium iodide (1.2 g) and dimethylsulfoxide (170 ml) were blended and warmed to 80° C. for 4 hours. After completion of the reaction, the resultant reaction solution was cooled to room temperature. To this, water (300 ml) and toluene (300 ml) were added and layers were separated. Subsequently, the organic layer was washed 5 times with a saturated aqueous sodium chloride solution (300 ml). After the resultant organic layer was dried over sodium sulfate, purification was performed by column chromatography using hexane as a developing solvent and silica gel as a filler to obtain compound MM-1 represented by the above formula MM-1.

ESI-MS: 460 [M]⁺

¹H-NMR (270 MHz, CDCl₃); δ=0.69 (t, 4H), 1.83 (m, 4H), 1.93 (m, 4H), 4.85 (d, 4H), 5.56 (m, 2H), 7.44-7.53 (m, 6H).

Synthesis Example 6 Synthesis of Compound MM-3

Under an argon atmosphere, in a 300 ml three-neck flask, 2,7-dibromofluorene (8.1 g), 8-bromo-1-octene (10.0 g), potassium hydroxide (6.0 g), potassium iodide (0.42 g) and dimethylsulfoxide (60 ml) were blended and warmed to 80° C. for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature. To this, water (100 ml) and toluene (100 ml) were blended. After layers were separated, the resultant organic layer was washed 5 times with a saturated aqueous sodium chloride solution (100 ml). After the resultant organic layer was dried over sodium sulfate, purification was performed by column chromatography using hexane as a developing solvent and silica gel as a filler to obtain compound MM-3 represented by the above formula MM-3.

ESI-MS: 544 [M]⁺

¹H-NMR (270 MHz, CDCl₃); δ=0.58 (m, 4H), 1.06 (m, 8H), 1.18 (m, 4H), 1.92 (m, 8H), 4.90 (d, 4H), 5.73 (m, 2H), 7.43-7.52 (m, 6H).

Synthesis Example 7 Synthesis of Compound MM-X

A 5 L-three-neck flask was purged with nitrogen. 1-Bromo-3-n-hexylbenzene (226 g) was weighed and dissolved in a 2.5 L dewatered THF. This solution was cooled to −75° C. or less and a 2.5 M n-butyllithium/hexane solution (358 ml) was added dropwise and stirred for 5 hours while the temperature was kept at −75° C. or less. To this solution, a solution of 2-methoxycarbonyl-4,4′-dibromobiphenyl (150 g) dissolved in 400 ml of dewatered THF was added dropwise while the temperature was kept at −70° C. or less. The solution was gradually increased to room temperature and then stirred overnight. While the reaction solution was stirred at 0° C., 150 ml of water was added dropwise. After a solvent was distilled away, water (200 ml) was added to the residue. Extraction was performed once with hexane (1 L) and twice with hexane (100 ml). Organic layers were combined and washed with a saturated saline solution (200 ml). The water layer was re-extracted with hexane (100 ml) and then, dried over magnesium sulfate. The solvent was distilled away to obtain a crude product (264 g) of compound MM-X and used in the next step without purification.

Note that 2-methoxycarbonyl-4,4′-dibromobiphenyl was synthesized by a method described in Journal of the American Chemical Society (1956), 78, 3196-3198.

Synthesis Example 8 Synthesis of Compound MM-Y

In a 3 L-three neck flask, compound MM-X (264 g) synthesized above was weighed, dissolved in dichloromethane (900 ml) and purged with nitrogen. This solution was cooled to 0° C. or less and a boron trifluoride diethyl ether complex (245 ml) was added dropwise while the temperature was kept at 5° C. or less. After the solution was slowly increased to room temperature, it was stirred overnight. This reaction solution was poured in a 2 L of ice water while stirring and stirred for 30 minutes. The layers were separated and the water layer was extracted with 100 ml of dichloromethane. Organic layers were combined and a 10% aqueous potassium phosphate solution (1 L) was added and then layers were separated. The organic layer was washed twice with water (1 L), dried over magnesium sulfate and then the solvent was distilled away. The resultant oil was dissolved in 200 ml of toluene and passed through a glass filter lined with silica gel to filtrate. After the solvent was distilled away, 500 ml of methanol was added and vigorously stirred. The resultant crystal was filtrated and washed with methanol. Recrystallization was performed from a solvent mixture of hexane/butyl acetate to obtain compound MM-Y (121 g).

¹H-NMR (300 MHz, CDCl₃); δ0.86 (6H, t), 1.26 (12H, m), 1.52 (4H, m), 2.51 (4H, t), 6.87 (2H, d), 7.00 (2H, s), 7.04 (2H, d), 7.12 (2H, t), 7.46 (2H, dd), 7.48 (2H, d), 7.55 (2H, d) ppm.

Synthesis Example 9 Synthesis of Compound MM-5

In a 2 L three-neck flask, compound MM-Y (50 g) was weighted and purged with nitrogen. Dewatered THF (500 ml) was added and cooled to −70° C. or less. While the solution was kept at −70° C. or less, a 2.5 M n-butyl lithium/hexane solution (68 ml) was added dropwise. After dropwise addition, the solution was stirred for 4 hours while keeping the temperature. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (44 ml) was added and then the solution was slowly increased to room temperature and stirred overnight. The solution was cooled to −30° C. and a 2 M hydrochloric acid/diethyl ether solution (78 ml) was added dropwise thereto and then the temperature of the solution was increased to room temperature. After the solvent was distilled away, the resultant substance was dissolved by adding toluene (400 ml) and filtrated by passing it through a glass filter lined with silica gel. When the solvent of the resultant solution was distilled away to obtain a crude product (50 g). Under a nitrogen atmosphere, recrystallization was performed from a toluene/acetonitrile solvent to obtain 34 g of compound MM-5.

¹H-NMR (300 MHz, CDCl₃); δ0.86 (6H, t), 1.26-1.29 (12H, m), 1.31 (24H, s), 1.52-1.53 (4H, m), 2.50 (4H, t), 6.92 (2H, d), 7.00 (2H, d), 7.08 (2H, t), 7.13 (2H, s), 7.77 (2H, d), 7.81-7.82 (4H, m) ppm.

Example 6 Synthesis of Polymer Compound P-1

Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.06 g), 2,7-dibromo-9,9-dioctylfluorene (0.22 g), bis(4-bromophenyl)-(4-sec-butylphenyl)-amine (0.55 g), compound M-4 (0.20 g), bis triphenylphosphine palladium dichloride (1.4 mg), trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were blended and heated to 105° C. To the resultant reaction solution, a 2 M aqueous sodium carbonate solution (6 ml) was added dropwise and refluxed for 15 hours. After completion of the reaction, phenylboric acid (240 mg) was added and refluxed for further 4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution (10 ml) was added and stirred at 80° C. for 4 hours. The resultant reaction solution was cooled to room temperature, then washed three times with water (30 ml), three times with a 3 wt % aqueous acetic acid solution (30 ml) and three times with water (30 ml), and purified by passing it through an alumina column and a silica gel column. The resultant toluene solution was added dropwise to methanol (300 ml) and stirred for one hour. Thereafter, the resultant solid substance was filtrated and dried to obtain polymer compound P-1 (0.7 g) represented by the following formula:

wherein the numbers attached outside parentheses each represent a molar ratio of a repeating unit.

The polystyrene-equivalent number average molecular weight of polymer compound P-1 was 1.1×10⁵ and the polystyrene-equivalent weight average molecular weight thereof was 3.8×10⁵.

Note that bis(4-bromophenyl)-(4-sec-butylphenyl)-amine was synthesized by a method described in WO2002/045184.

Example 7 Synthesis of Polymer Compound P-2

Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.05 g), 2,7-dibromo-9,9-dioctylfluorene (0.77 g), compound M-4 (0.31 g), bis triphenylphosphine palladium dichloride (1.4 mg), trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were blended and heated to 105° C. To the resultant reaction solution, a 2 M aqueous sodium carbonate solution (6 ml) was added dropwise and refluxed for 20 hours. After completion of the reaction, to this, phenylboric acid (240 mg) was added and refluxed for further 4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution (10 ml) was added and stirred at 80° C. for 4 hours. The resultant reaction solution was cooled to room temperature, then washed three times with water (30 ml), three times with a 3 wt % aqueous acetic acid solution (30 ml) and three times with water (30 ml), and purified by passing it through an alumina column and a silica gel column. The resultant toluene solution was added dropwise to methanol (300 ml) and stirred for one hour. Thereafter, the resultant solid substance was filtrated and dried to obtain polymer compound P-2 (0.8 g) represented by the following formula:

wherein the numbers attached outside parentheses each represent a molar ratio of a repeating unit.

The polystyrene-equivalent number average molecular weight of polymer compound P-2 was 4.1×10⁴ and the polystyrene-equivalent weight average molecular weight thereof was 1.3×10⁵.

Example 8 Synthesis of Polymer Compound P-3

Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.06 g), 2,7-dibromo-9,9-dioctylfluorene (0.66 g), N,N′-bis-(4-bromophenyl)-bis-(4-butylphenyl)-p-phenylenediamine (0.14 g), compound M-4 (0.20 g), compound MM-1 (0.09 g), palladium acetate (0.4 mg), tris(o-methoxyphenyl)phosphine (2.8 mg), trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were blended and heated to 105° C. To the resultant reaction solution, a 2 M aqueous sodium carbonate solution (11 ml) was added dropwise and refluxed for 18 hours. After completion of the reaction, to this, phenylboric acid (240 mg) was added and refluxed for further 4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution (10 ml) was added and stirred at 80° C. for 4 hours. The resultant reaction solution was cooled to room temperature, then washed three times with water (30 ml), three times with a 3 wt % aqueous acetic acid solution (30 ml) and three times with water (30 ml), and purified by passing it through an alumina column and a silica gel column. The resultant toluene solution was added dropwise to methanol (300 ml) and stirred for one hour. Thereafter, the resultant solid substance was filtrated and dried to obtain polymer compound P-3 (0.7 g) represented by the following formula:

wherein the numbers attached outside parentheses each represent a molar ratio of a repeating unit.

The polystyrene-equivalent number average molecular weight of polymer compound P-3 was 1.2×10⁵ and the polystyrene-equivalent weight average molecular weight thereof was 3.9×10⁵.

Example 9 Synthesis of Polymer Compound P-4

Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.05 g), 2,7-dibromo-9,9-dioctylfluorene (0.55 g), compound MM-4 (0.55 g) represented by the following formula (MM-4):

compound M-5 (0.09 g), palladium acetate (0.4 mg), tris(o-methoxyphenyl)phosphine (2.8 mg), trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were blended and heated to 105° C. To the resultant reaction solution, a 2 M aqueous sodium carbonate solution (11 ml) was added dropwise and refluxed for 22 hours. After completion of the reaction, to this, phenylboric acid (240 mg) was added and refluxed for further 4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution (10 ml) was added and stirred at 80° C. for 4 hours. The resultant reaction solution was cooled to room temperature, then washed three times with water (30 ml), three times with a 3 wt % aqueous acetic acid solution (30 ml) and three times with water (30 ml), and purified by passing it through an alumina column and a silica gel column. The resultant toluene solution was added dropwise to methanol (300 ml) and stirred for one hour. Thereafter, the resultant solid substance was filtrated and dried to obtain polymer compound P-5 (0.7 g) represented by the following formula:

wherein the numbers attached outside parentheses each represent a molar ratio of a repeating unit.

The polystyrene-equivalent number average molecular weight of polymer compound P-5 was 4.2×10⁴ and the polystyrene-equivalent weight average molecular weight thereof was 7.5×10⁴.

Note that compound MM-4 was synthesized by a method described in EP1310539.

Example 10 Synthesis of Polymer Compound P-5

Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.06 g), 2,7-dibromo-9,9-dioctylfluorene (0.66 g), compound M-7 (0.55 g), palladium acetate (0.4 mg), tris(o-methoxyphenyl)phosphine (2.8 mg), trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were blended and heated to 105° C. To the resultant reaction solution, a 2 M aqueous sodium carbonate solution (11 ml) was added dropwise and refluxed for 4 hours. After completion of the reaction, to this, phenylboric acid (240 mg) was added and refluxed for further 4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution (10 ml) was added and stirred at 80° C. for 4 hours. The resultant reaction solution was cooled to room temperature, then washed three times with water (30 ml), three times with a 3 wt % aqueous acetic acid solution (30 ml) and three times with water (30 ml), and purified by passing it through an alumina column and a silica gel column. The resultant toluene solution was added dropwise to methanol (300 ml) and stirred for one hour. Thereafter, the resultant solid substance was filtrated and dried to obtain polymer compound P-6 (0.9 g) represented by the following formula:

wherein the numbers attached outside parentheses each represent a molar ratio of a repeating unit.

The polystyrene-equivalent number average molecular weight of polymer compound P-6 was 1.0×10⁵ and the polystyrene-equivalent weight average molecular weight thereof was 3.9×10⁵.

Example 11 Synthesis of Polymer Compound P-6

Under an inert gas atmosphere, the compound (1.48 g) represented by the following formula (MM-5):

2,7-dibromo-9,9-dioctylfluorene (0.22 g), the compound (0.82 g) represented by the above formula (MM-4), compound (M-9) (0.23 g), palladium acetate (0.4 mg), tris(o-methoxyphenyl)phosphine (2.8 mg) and toluene (44 ml) were blended and heated to 105° C. To the resultant reaction solution, a 20% aqueous tetraethyl ammonium hydroxide solution (6.6 ml) was added dropwise and refluxed for 4 hours. After completion of the reaction, to this, phenylboric acid (240 mg) was added and refluxed for further 18 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution (22 ml) was added and stirred at 80° C. for 4 hours. The resultant reaction solution was cooled to room temperature, then washed three times with water (30 ml), three times with a 3 wt % aqueous acetic acid solution (30 ml) and three times with water (30 ml), and purified by passing it through an alumina column and a silica gel column. The resultant toluene solution was added dropwise to methanol (300 ml) and stirred for one hour and thereafter, the resultant solid substance was filtrated and dried to obtain polymer compound P-6 (1.5 g) represented by the following formula:

wherein the numbers attached outside parentheses each represent a molar ratio of a repeating unit.

The polystyrene-equivalent number average molecular weight of polymer compound P-6 was 2.2×10⁵ and the polystyrene-equivalent weight average molecular weight thereof was 8.5×10⁵.

Example 12 Synthesis of Polymer Compound P-7

Under an inert gas atmosphere, the compound (1.48 g) represented by the above formula (MM-5), 2,7-dibromo-9,9-dioctylfluorene (0.22 g), the compound (0.82 g) represented by the above formula (MM-4), compound (M-4) (0.20 g), palladium acetate (0.4 mg), tris(o-methoxyphenyl)phosphine (2.8 mg) and toluene (44 ml) were blended and heated to 105° C. To the resultant reaction solution, a 20% aqueous tetraethyl ammonium hydroxide solution (6.6 ml) was added dropwise and refluxed for 18 hours. After completion of the reaction, to this, phenylboric acid (240 mg) was added and refluxed for further 4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution (22 ml) was added and stirred at 80° C. for 4 hours. The resultant reaction solution was cooled to room temperature, then washed three times with water (30 ml), three times with a 3 wt % aqueous acetic acid solution (30 ml) and three times with water (30 ml), and purified by passing it through an alumina column and a silica gel column. The resultant toluene solution was added dropwise to methanol (300 ml) and stirred for one hour and thereafter, the resultant solid substance was filtrated and dried to obtain polymer compound P-7 (1.3 g) represented by the following formula:

wherein the numbers attached outside parentheses each represent a molar ratio of a repeating unit.

The polystyrene-equivalent number average molecular weight of polymer compound P-7 was 5.1×10⁴ and the polystyrene-equivalent weight average molecular weight thereof was 1.0×10⁵.

Comparative Example 1 Synthesis of Polymer Compound CP-1

Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.06 g), bis(4-bromophenyl)-(4-sec-butylphenyl)-amine (0.87 g), compound MM-6 (0.04 g) represented by the following formula (MM-6):

bis triphenylphosphine palladium dichloride (1.4 mg), trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were blended and heated to 105° C. To the resultant reaction solution, a 2 M aqueous sodium carbonate solution (6 ml) was added dropwise and refluxed for 7 hours. After completion of the reaction, to this, phenylboric acid (240 mg) was added and refluxed for further 4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution (10 ml) was added and stirred at 80° C. for 4 hours. The resultant reaction solution was cooled to room temperature, then washed three times with water (30 ml), three times with a 3 wt % aqueous acetic acid solution (30 ml) and three times with water (30 ml), and purified by passing it through an alumina column and a silica gel column. The resultant toluene solution was added dropwise to methanol (300 ml) and stirred for one hour. Thereafter, the resultant solid substance was filtrated and dried to obtain polymer compound CP-1 (0.8 g) represented by the following formula:

wherein the numbers attached outside parentheses each represent a molar ratio of a repeating unit.

The polystyrene-equivalent number average molecular weight of polymer compound CP-1 was 3.4×10⁴ and the polystyrene-equivalent weight average molecular weight thereof was 6.7×10⁴.

Note that compound MM-6 was synthesized by a method described in US2004/035221.

Comparative Example 2 Synthesis of Polymer Compound CP-2

Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.06 g), 2,7-dibromo-9,9-dioctylfluorene (0.22 g), bis(4-bromophenyl)-(4-sec-butylphenyl)-amine (0.55 g), compound MM-2 (0.21 g) represented by the following formula (MM-2):

bis triphenylphosphine palladium dichloride (1.4 mg), trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were blended and heated to 105° C. To the resultant reaction solution, a 2 M aqueous sodium carbonate solution (6 ml) was added dropwise and refluxed for 7 hours. After completion of the reaction, to this, phenylboric acid (240 mg) was added and refluxed for further 4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution (10 ml) was added and stirred at 80° C. for 4 hours. The resultant reaction solution was cooled to room temperature, then washed three times with water (30 ml), three times with a 3 wt % aqueous acetic acid solution (30 ml) and three times with water (30 ml) and purified by passing it through an alumina column and a silica gel column. The resultant toluene solution was added dropwise to methanol (300 ml) and stirred for one hour. Thereafter, the resultant solid substance was filtrated and dried to obtain polymer compound CP-2 (yield 0.9 g) represented by the following formula:

wherein the numbers attached outside parentheses each represent a molar ratio of a repeating unit.

The polystyrene-equivalent number average molecular weight of polymer compound CP-2 was 8.4×10⁴ and the polystyrene-equivalent weight average molecular weight thereof was 2.0×10⁵.

Note that compound MM-2 was synthesized by a method described in JP 2008-106241 A.

Comparative Example 3 Synthesis of Polymer Compound CP-3

Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.06 g), compound MM-3 (0.22 g) represented by the above formula MM-3, N,N-di(4-bromophenyl)aniline (0.73 g), bis triphenylphosphine palladium dichloride (1.4 mg), trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were blended and heated to 105° C. To the resultant reaction solution, a 2 M aqueous sodium carbonate solution (6 ml) was added dropwise and refluxed for 20 hours. After completion of the reaction, phenylboric acid (240 mg) was added and refluxed for further 4 hours. Subsequently, a 1.8 M aqueous sodium diethyldithiacarbamate solution (10 ml) was added and stirred at 80° C. for 4 hours. The resultant reaction solution was cooled to room temperature, then washed three times with water (30 ml), three times with a 3 wt % aqueous acetic acid solution (30 ml) and three times with water (30 ml) and purified by passing it through an alumina column and a silica gel column. The resultant toluene solution was added dropwise to methanol (300 ml) and stirred for one hour and thereafter, the resultant solid substance was filtrated and dried to obtain polymer compound CP-3 (0.8 g) represented by the following formula:

wherein the numbers attached outside parentheses each represent a molar ratio of a repeating unit.

The polystyrene-equivalent number average molecular weight of polymer compound CP-3 was 5.3×10⁴ and the polystyrene-equivalent weight average molecular weight thereof was 1.9×10⁵.

Synthesis Example 10 Synthesis of Polymer Compound P-8

Under an inert gas atmosphere, compound MM-8 (7.28 g) represented by the following formula MM-8:

2,7-dibromo-9,9-dioctylfluorene (4.94 g), compound MM-9 (0.74 g), represented by the following formula MM-9:

bis triphenylphosphine palladium dichloride (7.0 mg), trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich) (1.30 g) and toluene (100 ml) were blended and heated to 105° C. To the resultant reaction solution, a 2 M aqueous sodium carbonate solution (27 ml) was added dropwise and refluxed for 2 hours. After completion of the reaction, phenylboric acid (120 mg) was added and refluxed for further 4 hours. Subsequently, a 1.8 M aqueous sodium diethyldithiacarbamate solution (60 ml) was added and stirred at 80° C. for 4 hours. The resultant reaction solution was cooled to room temperature, then washed three times with water (130 ml), three times with a 3 wt % aqueous acetic acid solution (130 ml) and three times with water (130 ml) and purified by passing it through an alumina column and a silica gel column. The resultant toluene solution was added dropwise to methanol (1.5 L) and stirred for one hour. Thereafter, the resultant solid substance was filtrated and dried to obtain polymer compound P-8 (8.0 g) represented by the following formula:

wherein the numbers attached outside parentheses each represent a molar ratio of a repeating unit.

The polystyrene-equivalent number average molecular weight of polymer compound P-8 was 5.1×10⁴ and the polystyrene-equivalent weight average molecular weight thereof was 1.4×10⁵.

Note that compound MM-8 represented by the above formula MM-8 was synthesized by a method described in WO2008111658.

Furthermore, compound MM-9 represented by the above formula MM-9 was synthesized by a method described in EP1394188.

<Preparation of Liquid Composition>

Compound M-7, polymer compounds P-1 to P-7 and polymer compounds CP-1 to CP-3 were each dissolved in xylene. In this manner, a liquid composition containing about 1 wt % of each of the compounds was prepared.

<Evaluation of Residual Film Rate on Glass Substrate>

The liquid composition was added dropwise onto a glass substrate by a spin coater (trade name: MS-A100 type, manufactured by Misawa) in the condition of 1000 rpm for 15 seconds. The film thickness (H₁) of the resultant film was measured by a profiler (trade name: P-16+, manufactured by KLA-Tencor Corporation).

Subsequently, in a globe box purged with nitrogen, the film on the glass substrate was baked by use of a high power hot plate (trade name: HP-ISA, manufactured by AS ONE Corporation), at a baking temperature shown in Table 1 for 20 minutes. The resultant film on the glass substrate was cooled to room temperature, then soaked in a xylene solution and then rinsed by a spin coater (trade name: MS-A100 type, manufactured by Misawa) in the conditions of 1000 rpm for 15 seconds. The film thickness (H₂) of the film produced was measured by the profiler (trade name: P-16+, manufactured by KLA-Tencor Corporation).

A value of (H₂)/(H₁) was defined as a residual film rate and the results obtained are shown in Table 1.

TABLE 1 Residual film rate 130° C. 150° C. 170° C. 190° C. Compound Bake Bake Bake Bake Example 13 M-7 44% 54% 84% 99% Example 14 P-1 96% 96% 99% 99% Example 15 P-2 74% 88% 92% 96% Example 16 P-3 83% 85% 96% 97% Example 17 P-4 22% 38% 52% 74% Example 18 P-5 59% 68% 82% 89% Example 19 P-6 74% 90% 98% 99% Example 20 P-7 63% 87% 91% 99% Comparative CP-1 0% 0% 0% 10% Example 4 Comparative CP-2 0% 0% 0% 53% Example 5 Comparative CP-3 0% 0% 38% 51% Example 6

<Evaluation>

Compound M-7 and polymer compounds P-1 to P-7 were each confirmed to have high harden ability compared to polymer compounds CP-1 to CP-3. Furthermore, even in the range as low as 130° C. to 150° C. compared to 190° C., compound M-7 and polymer compounds P-1 to P-7 exhibited harden ability.

<Production and Evaluation of Electroluminescence (EL) Device>

Example 21

Preparation of Polymer Compound <P-5> Solution

The polymer compound <P-5> obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.2 wt %.

Preparation of Polymer Compound <P-8> Solution

The polymer compound <P-8> obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.2 wt %.

Production of EL Device

On a glass substrate to which an ITO film of 150 nm in thickness was attached by a sputtering method, a suspension solution of poly(3,4)ethylenedioxythiophene/polystyrene sulfonate (Baytron P AI4083 manufactured by Bayer) previously filtrated by a 0.2 μm membrane filter, was applied by spin coating to form a film of 70 nm in thickness and dried on a hot plate at 200° C. for 10 minutes. Subsequently, using a xylene solution of the polymer compound <P-5> obtained above, a film was formed by spin coating at a rotation rate of 1600 rpm and heated on a hot plate at 150° C. for 20 minutes to harden the film. After completion of film formation, the thickness of the film was about 20 nm. Furthermore, using a xylene solution of the polymer compound <P-8> obtained above, a film was formed by spin coating at a rotation rate of 1500 rpm. After the film formation, the thickness of the film was about 60 nm. Furthermore, this was dried under reduced pressure at 130° C. for 10 minutes, and thereafter barium was vapor-deposited as a cathode in a thickness of about 5 nm, and then aluminum was vapor-deposited in a thickness of about 100 nm to produce an EL device. Note that vapor deposition of a metal was initiated after a degree of vacuum reached 1×10⁻⁴ Pa or less.

Performance of EL Device

When voltage was applied to the resultant device, EL emission having a peak at 460 nm was provided from the device.

The time (life) for reducing a degree of brightness from the initial brightness (100 cd/m²) to a half (50%) was as long as 26 hours.

Example 22

Preparation of Polymer Compound <P-6> Solution

The polymer compound <P-6> obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.2 wt %.

Preparation of Polymer Compound <P-8> Solution

The polymer compound <P-8> obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.2 wt %.

Production of EL Device

On a glass substrate to which an ITO film of 150 nm in thickness was attached by a sputtering method, a suspension solution of poly(3,4)ethylenedioxythiophene/polystyrene sulfonate (Baytron P AI4083 manufactured by Bayer) previously filtrated by a 0.2 μm membrane filter, was applied by spin coating to form a film of 70 nm in thickness and dried on a hot plate at 200° C. for 10 minutes. Subsequently, using a xylene solution of the polymer compound <P-6> obtained above, a film was formed by spin coating at a rotation rate of 1600 rpm and heated on a hot plate at 150° C. for 20 minutes to harden the film. After the film formation, the thickness of the film was about 20 nm. Furthermore, using a xylene solution of the polymer compound <P-8> obtained above, a film was formed by spin coating at a rotation rate of 1500 rpm. After completion of film formation, the thickness of the film was about 60 nm. Furthermore, this was dried under reduced pressure at 130° C. for 10 minutes, and thereafter barium was vapor-deposited as a cathode in a thickness of about 5 nm, and then aluminum was vapor-deposited in a thickness of about 100 nm to produce an EL device. Note that vapor deposition of a metal was initiated after a degree of vacuum reached 1×10⁻⁴ Pa or less.

Performance of EL Device

When voltage was applied to the resultant device, EL emission having a peak at 470 nm was provided from the device.

The time (life) for reducing a degree of brightness from the initial brightness (100 cd/m²) to a half (50%) was as long as 22 hours.

Comparative Example 7

Preparation of Polymer Compound <CP-1> Solution

The polymer compound <CP-1> obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.2 wt %.

Production of EL Device

On a glass substrate to which an ITO film of 150 nm in thickness was attached by a sputtering method, a suspension solution of poly(3,4)ethylenedioxythiophene/polystyrene sulfonate (Baytron P AI4083 manufactured by Bayer) previously filtrated by a 0.2 μm membrane filter was applied by spin coating to form a film of 70 nm in thickness and dried on a hot plate at 200° C. for 10 minutes. Subsequently, using a xylene solution of the polymer compound <CP-1> obtained above, a film was formed by spin coating at a rotation rate of 1600 rpm and heated on a hot plate at 150° C. for 20 minutes to harden the film. After completion of film formation, the thickness of the film was about 20 nm. Furthermore, using a xylene solution of the polymer compound <P-8> obtained above, a film was formed by spin coating at a rotation rate of 1500 rpm. After the film formation, the thickness of the film was about 60 nm. Furthermore, this was dried under reduced pressure at 130° C. for 10 minutes, and thereafter barium was vapor-deposited as a cathode in a thickness of about 5 nm, and then aluminum was vapor-deposited in a thickness of about 100 nm to produce an EL device. Note that vapor deposition of a metal was initiated after a degree of vacuum reached 1×10⁻⁴ Pa or less.

Performance of EL Device

When voltage was applied to the resultant device, EL emission having a peak at 460 nm was provided from the device.

The time (life) for reducing a degree of brightness from the initial brightness (100 cd/m²) to a half (50%) was one hour.

Comparative Example 8

Preparation of Polymer Compound <CP-2> Solution

The polymer compound <CP-2> obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.2 wt %.

Production of EL Device

On a glass substrate to which an ITO film of 150 nm in thickness was attached by a sputtering method, a suspension solution of poly(3,4)ethylenedioxythiophene/polystyrene sulfonate (Baytron P AI4083 manufactured by Bayer) previously filtrated by a 0.2 μm membrane filter was applied by spin coating to form a film of 70 nm in thickness and dried on a hot plate at 200° C. for 10 minutes. Subsequently, using a xylene solution of the polymer compound <CP-2> obtained above, a film was formed by spin coating at a rotation rate of 1600 rpm and heated on a hot plate at 150° C. for 20 minutes to harden the film. After completion of film formation, the thickness of the film was about 20 nm. Furthermore, using a xylene solution of the polymer compound <P-8> obtained above, a film was formed by spin coating at a rotation rate of 1500 rpm. After the film formation, the thickness of the film was about 60 nm. Furthermore, this was dried under reduced pressure at 130° C. for 10 minutes, and thereafter barium was vapor-deposited as a cathode in a thickness of about 5 nm, and then aluminum was vapor-deposited in a thickness of about 100 nm to produce an EL device. Note that vapor deposition of a metal was initiated after a degree of vacuum reached 1×10⁻⁴ Pa or less.

Performance of EL Device

When voltage was applied to the resultant device, EL emission having a peak at 460 nm was provided from the device.

The time (life) for reducing a degree of brightness from the initial brightness (100 cd/m²) to a half (50%) was 14 hours.

Comparative Example 9

Preparation of Polymer Compound <CP-3> Solution

The polymer compound <CP-3> obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.2 wt %.

Production of EL Device

On a glass substrate to which an ITO film of 150 nm in thickness was attached by a sputtering method, a suspension solution of poly(3,4)ethylenedioxythiophene/polystyrene sulfonate (Baytron P AI4083 manufactured by Bayer) filtrated by a 0.2 μm membrane filter was applied by spin coating to form a film of 70 nm in thickness and dried on a hot plate at 200° C. for 10 minutes. Subsequently, using a xylene solution of the polymer compound <CP-3> obtained above, a film was formed by spin coating at a rotation rate of 1600 rpm and heated on a hot plate at 150° C. for 20 minutes to harden the film. After completion of film formation, the thickness of the film was about 20 nm. Furthermore, using a xylene solution of the polymer compound <P-8> obtained above, a film was formed by spin coating at a rotation rate of 1500 rpm. After completion of film formation, the thickness of the film was about 60 nm. Furthermore, this was dried under reduced pressure at 130° C. for 10 minutes, and thereafter barium was vapor-deposited as a cathode in a thickness of about 5 nm, and then aluminum was vapor-deposited in a thickness of about 100 nm to produce an EL device. Note that vapor deposition of a metal was initiated after a degree of vacuum reached 1×10⁻⁴ Pa or less.

Performance of EL Device

When voltage was applied to the resultant device, EL emission having a peak at 460 nm was provided from the device.

The time (life) for reducing a degree of brightness from the initial brightness (100 cd/m²) to a half (50%) was 11 hours.

Industrial Applicability

A compound containing a 1,3-diene structure of the present invention can be used as a material and the like for use in an organic layer of a light-emitting device. 

The invention claimed is:
 1. A compound comprising a group represented by the following formula (I):

wherein Ar¹ represents an arylene group, a heterocyclic group or an aromatic amine group, the arylene group, the heterocyclic group or the aromatic amine group represented by Ar¹ being attached to a group represented by formula (Ia):

J¹ represents a phenylene group; J² represents an alkylene group; X represents an oxygen atom or a sulfur atom; j is 1, k is an integer of 0 to 3 and 1 is 0 or 1, such that 1 ≦j+k+1≦5; m is 1 or 2; R¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, a carbamoyl group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group; a plurality of R¹ may be the same or different; and a plurality of J¹, J², X, j, k and l each may be the same or different; and the compound having a group represented by the above formula (I) is a polymer compound having a group represented by the above formula (I) as a repeating unit.
 2. The compound according to claim 1, wherein R¹ is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group or a cyano group.
 3. The compound according to claim 1, wherein Ar¹ is a phenylene group or a fluorene-diyl group, which is attached to a group represented by the formula (Ia).
 4. The compound according to claim 1, wherein Ar¹ is a group represented by the following formula (II):

wherein Y represents an oxygen atom, a sulfur atom, —N(R22)—,—O——C(R²³)(R²⁴)—, or —Si(R²⁵)(R²⁶)—; R²², R²³, R²⁴, R²⁵ and R²⁶ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an arylalkyl group; and the formula may have a substituent; and the group represented by Ar¹ is attached to a group represented by the formula (Ia).
 5. The compound according to claim 1, wherein Ar¹ is a group represented by the following formula (III):

wherein R³ represents a hydrogen atom, an alkyl group, an alkoxy group or a substituted amino group; five R³ may be the same or different, or a group represented by the following formula (IV):

wherein R⁴ represents a hydrogen atom, an alkyl group, an alkoxy group or a substituted amino group; and ten R⁴ may be the same or different, and the group represented by Ar¹ is attached to a group represented by the formula (Ia).
 6. The compound according to claim 1, wherein in the above formula (I), the group represented by the following formula (Ia):

wherein j, k, l, J¹, J² and R¹ are the same as defined above, is a group represented by the following formula (Ib):

wherein k, l, J² and R¹ are the same as defined above.
 7. The compound according to claim 6, wherein the group represented by the above formula (Ib) is a group represented by the following formula (Ic):

wherein k, l and J² are the same as defined above, or a group represented by the following formula (Id):

wherein k, l and J² are the same as defined above.
 8. The compound according to claim 1, further comprising a repeating unit represented by the following formula (A):

wherein Ar² represents an arylene group, a heterocyclic group or an aromatic amine group; J³ represents a direct bond, an alkylene group or a phenylene group; n represents 1 or 2; a plurality of J³ may be the same or different.
 9. The compound according to claim 8, wherein Ar² is an arylene group, J³ is a direct bond and n is
 2. 10. The compound according to claim 8, further comprising a repeating unit represented by the following formula (C):

wherein R⁶ represents an alkyl group, an aryl group, an arylalkyl group or an arylalkoxy group; and two R⁶ may be the same or different.
 11. The compound according to claim 8, having a polystyrene-equivalent number average molecular weight of 1×10³ to 1×10⁸.
 12. The compound according to claim 1, further comprising a repeating unit represented by the following formula (B):

wherein Ar³ represents an arylene group, a heterocyclic group or an aromatic amine group; J⁴ represents a direct bond, an alkylene group or a phenylene group; R⁵ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, a carbamoyl group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group; o represents 1 or 2; a plurality of R⁵ may be the same or different; and a plurality of J⁴ may be the same or different.
 13. The compound according to claim 12, wherein Ar³ is an arylene group, J⁴ is an alkylene group, and o is
 2. 14. The compound according to claim 1, further comprising a repeating unit represented by the following formula (C):

wherein R⁶ represents an alkyl group, an aryl group, an arylalkyl group or an arylalkoxy group; and two R⁶ may be the same or different.
 15. The compound according to claim 14, wherein R⁶ is an alkyl group, an aryl group or an arylalkyl group.
 16. The compound according to claim 1, having a polystyrene-equivalent number average molecular weight of 1×10³ to 1×10⁸.
 17. A composition comprising at least one selected from the group consisting of a hole transport material, an electron transport material and a light-emitting material and the compound according to claim
 1. 18. A liquid composition containing the compound according to claim 1 and a solvent.
 19. A film containing the compound according to claim
 1. 20. A film obtained by cros slinking the compound according to claim
 1. 21. A light-emitting device having electrodes comprising an anode and a cathode and an organic layer formed between the electrodes and containing the compound according to claim
 1. 22. The light-emitting device according to claim 21, wherein the organic layer is a light-emitting layer or a charge transport layer.
 23. A surface light source comprising the light-emitting device according to claim
 21. 24. A display comprising the light-emitting device according to claim
 21. 25. An organic transistor formed of the compound according to claim
 1. 26. An organic photoelectric transducer formed of the compound according to claim
 1. 